Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method

ABSTRACT

To provide a fluorinated ether compound capable of forming a surface layer excellent in initial water/oil repellency, fingerprint stain removability, abrasion resistance and light resistance; a fluorinated ether composition and a coating liquid containing the fluorinated ether compound; an article having a surface layer excellent in initial water/oil repellency, fingerprint stain removability, abrasion resistance and light resistance and a method for producing it. A fluorinated ether compound having a poly(oxyperfluoroalkylene) chain having a unit (α) which is an oxyperfluoroalkylene unit having 5 or 6 carbon atoms, and a unit (β) which is an oxyperfluoroalkylene unit having at most 4 carbon atoms, and having at least one of a hydrolysable silyl group and a silanol group on at least one terminal of the poly(oxyperfluoroalkylene) chain via a linking group.

TECHNICAL FIELD

The present invention relates to a fluorinated ether compound, afluorinated ether composition, a coating liquid, an article and itsproduction method.

BACKGROUND ART

A fluorinated ether compound having a poly(oxyperfluoroalkylene) chainis capable of forming on a surface of a substrate a surface layer havinghigh lubricity, water/oil repellency, etc. and thus is suitably used fora surface treatment agent. A surface treatment agent containing thefluorinated ether compound is used in an application where it is desiredto maintain, for a long period of time, a performance (abrasionresistance) whereby water/oil repellency is less likely to be loweredeven if the surface layer is rubbed repeatedly with a finger, and aperformance (fingerprint stain removability) whereby a fingerprintadhering to the surface layer can be readily removed by wiping, forexample, as a surface treatment agent for a member constituting thesurface of a touch panel to be touched with a finger.

As a fluorinated ether compound which is capable of forming on a surfaceof a substrate a surface layer excellent in abrasion resistance andfingerprint stain removability, the following has been proposed.

A fluorinated ether compound which has a poly(oxyperfluoroalkylene)chain (αβ) having a C₄ oxyperfluoroalkylene unit (α) and anoxyperfluoroalkylene unit (β) other than the unit (α) and which has ahydrolyzable silyl group on at least one terminal of thepoly(oxyperfluoroalkylene) chain (αβ) via a linking group (PatentDocument 1).

PRIOR ART DOCUMENTS Patent Document

Patent Document 1: WO2013/121986

DISCLOSURE OF INVENTION Technical Problem

In recent years, a surface layer of a member constituting a surface tobe touched by fingers of a touch panel is required to have furtherimproved abrasion resistance and light resistance. Accordingly, afluorinated ether compound capable of forming a surface layer excellentin fingerprint stain removability, abrasion resistance and lightresistance may sometimes be required.

An object of the present invention is to provide a fluorinated ethercompound capable of forming a surface layer excellent in initialwater/oil repellency, fingerprint stain removability, abrasionresistance and light resistance; a fluorinated ether composition and acoating liquid containing the fluorinated ether compound; an articlehaving a surface layer excellent in initial water/oil repellency,fingerprint stain removability, abrasion resistance and light resistanceand a method for producing it.

Another object of the present invention is to provide a fluorinatedether compound useful as an intermediate of a fluorinated ether compoundsuitably used for a surface treatment agent.

Solution to Problem

The present invention provides a fluorinated ether compound, afluorinated ether composition, a coating liquid, an article and a methodfor producing the article, having the following constructions [1] to[15].

-   [1] A fluorinated ether compound having a poly(oxyperfluoroalkylene)    chain having a unit (α) which is an oxyperfluoroalkylene unit having    5 or 6 carbon atoms, and a unit (β) which is an oxyperfluoroalkylene    unit having at most 4 carbon atoms, and having at least one of a    hydrolyzable silyl group and a silanol group on at least one    terminal of the poly(oxyperfluoroalkylene) chain via a linking    group.-   [2] The fluorinated ether compound according to [1], wherein in the    poly(oxyperfluoroalkylene) chain, the proportion of the number of    the unit (α) to the total number of the unit (α) and the unit (β) is    from 0.02 to 0.5.-   [3] The fluorinated ether compound according to [1] or [2], wherein    the poly(oxyperfluoroalkylene) chain contains a structure having the    unit (α) and the unit (β) alternately arranged.-   [4] The fluorinated ether compound according to any one of [1] to    [3], wherein the unit (α) is (CF₂CF₂CF₂CF₂CF₂O) or    (CF₂CF₂CF₂CF₂CF₂CF₂O).-   [5] The fluorinated ether compound according to any one of [1] to    [4], wherein the unit (β) is (CF₂O) or (CF₂CF₂O).-   [6] The fluorinated ether compound according to any one of [1] to    [5], which is a compound represented by the following formula (11):    A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B¹  (11)

wherein A¹ is a C₁₋₂₀ perfluoroalkyl group or B¹,

R^(f1) is a C₁ perfluoroalkylene group,

R^(f2) is a C₂ perfluoroalkylene group,

R^(f3) is a C₃ perfluoroalkylene group,

R^(f4) is a C₄ perfluoroalkylene group,

R^(f5) is a C₅ perfluoroalkylene group,

R^(f6) is a C₆ perfluoroalkylene group,

m1, m2, m3, m4, m5 and m6 are each 0 or an integer of at least 1,m1+m2+m3+m4 is an integer of at least 1, m5+m6 is an integer of at least1, and m1+m2+m3+m4+m5+m6 is an integer of from 2 to 200,

B¹ is -Q[-SiR_(n)L_(3-n)]_(k),

Q is a (k+1) valent linking group,

R is a hydrogen atom or a monovalent hydrocarbon group,

L is a hydrolyzable group or a hydroxy group,

n is an integer of from 0 to 2, and

k is an integer of from 1 to 10.

-   [7] The fluorinated ether compound according to [6], wherein B¹ is a    group represented by any one of the following formulae (g1) to (g7):    —R^(f7)—(X¹)_(p)-Q¹-SiR_(n)L_(3-n)  (g1)    —R^(f7)—(X²)_(r)-Q²¹-N[-Q²²-SiR_(n)L_(3-n)]₂  (g2)    —R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-O)_(t)—C[—(O)_(u)-Q³²-SiR_(n)L_(3-n)]₃  (g3)    —R^(f7)-Q⁴¹-Si[-Q⁴²-SiR_(n)L_(3-n)]₃  (g4)    —R^(f7)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q⁵²-SiR_(n)L_(3-n)]_(w)  (g5)    —R^(f7)-Q⁶¹-G(R⁶)[-Q⁶²-SiR_(n)L_(3-n)]₂  (g6)    —R^(f7)-Q⁷¹-[CH₂C(R⁷¹)(-Q⁷²-SiR_(n)L_(3-n)]_(y)-R⁷²  (g7)

wherein R^(f7) is a C₁₋₆ perfluoroalkylene group,

R is a hydrogen atom or a monovalent hydrocarbon group,

L is a hydrolyzable group or a hydroxy group,

n is an integer of from 0 to 2,

in the formula (g1),

X¹ is an etheric oxygen atom or —C(O)N(R¹)— (provided that N is bondedto Q¹),

R¹ is a hydrogen atom or an alkyl group,

p is 0 or 1, and

Q¹ is an alkylene group, a group having an etheric oxygen atom or asilphenylene skeleton between carbon atoms of an alkylene group havingat least 2 carbon atoms, or a group having a bivalent organopolysiloxaneresidue or a dialkylsilylene group between carbon atoms or at a terminalon the side bonded to (X¹)_(p) of an alkylene group having at least 2carbon atoms,

in the formula (g2),

X² is an etheric oxygen atom, —NH— or —C(O)N(R²)— (provided that N isbonded to Q²¹),

R² is a hydrogen atom or an alkyl group,

r is 0 or 1 (provided that it is 0 when Q²¹ is a single bond),

Q²¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom, —NH—, —C(O)—, —C(O)O— or —OC(O)— between carbon atoms of analkylene group having at least 2 carbon atoms,

Q²² is an alkylene group, or a group having an etheric oxygen atom, —NH—or a bivalent organopolysiloxane residue between carbon atoms of analkylene group having at least 2 carbon atoms, and

two [-Q²²-SiR_(n)L_(3-n)] may be the same or different,

in the formula (g3),

R³¹ is a hydrogen atom or an alkyl group,

s is 0 or 1,

Q³¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

t is 0 or 1 (provided that it is 0 when Q³¹ is a single bond),

u is 0 or 1,

Q³² is an alkylene group, a group having an etheric oxygen atom or asilphenylene skeleton between carbon atoms of an alkylene group havingat least 2 carbon atoms, or a group having —C(O)N(R³²)—, a bivalentorganopolysiloxane residue or a dialkylsilylene group between carbonatoms or at a terminal on the side bonded to (O)_(u) of an alkylenegroup having at least 2 carbon atoms,

R³² is a hydrogen atom or an alkyl group, and

three [—(O)_(u)-Q³²-SiR_(n)L_(3-n)] may be the same or different,

in the formula (g4),

Q⁴¹ is an alkylene group, or a group having an etheric oxygen atombetween carbon atoms of an alkylene group having at least 2 carbonatoms,

Q⁴² is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms, and

three [-Q⁴²-SiR_(n)L_(3-n)] may be the same or different,

in the formula (g5),

R⁵ is a hydrogen atom or an alkyl group,

v is 0 or 1,

Q⁵¹ is an alkylene group, or a group having an etheric oxygen atombetween carbon atoms of an alkylene group having at least 2 carbonatoms,

Z is a (w+1) valent organopolysiloxane residue,

Q⁵² is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms,

w is an integer of from 2 to 7, and

w [-Q⁵²-SiR_(n)L_(3-n)] may be the same or different,

in the formula (g6),

Q⁶¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

G is a carbon atom or a silicon atom,

R⁶ is a hydroxy group or an alkyl group,

Q⁶² is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms, and

two [-Q⁶²-SiR_(n)L_(3-n)] may be the same or different, and

in the formula (g7),

Q⁷¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

R⁷¹ is a hydrogen atom or an alkyl group,

Q⁷² is a single bond or an alkylene group,

R⁷² is a hydrogen atom or a halogen atom,

y is an integer of from 1 to 10, and

two to ten [-Q⁷²-SiR_(n)L_(3-n)] may be the same or different.

-   [8] The fluorinated ether compound according to [6] or [7], wherein    in the formula (11), A¹ is a C₁₋₂₀ perfluoroalkyl group, and all the    (R^(f5)O) and (R^(f6)O) are located on the A¹-O— side from the    [0.5×(m1+m2+m3+m4+m5+m6)]th unit as counted from the A¹-O— side.-   [9] The fluorinated ether compound according to any one of [1] to    [5], which is a compound represented by the following formula (10):    [A¹⁰-O—{(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)}]_(j)—B¹⁰  (10)

wherein A¹⁰ is a C₁₋₂₀ perfluoroalkyl group or B¹⁰,

R^(f1) is a C₁ perfluoroalkylene group,

R^(f2) is a C₂ perfluoroalkylene group,

R^(f3) is a C₃ perfluoroalkylene group,

R^(f4) is a C₄ perfluoroalkylene group,

R^(f5) is a C₅ perfluoroalkylene group,

R^(f6) is a C₆ perfluoroalkylene group,

m1, m2, m3, m4, m5 and m6 are each 0 or an integer of at least 1,m1+m2+m3+m4 is an integer of at least 1, m5+m6 is an integer of at least1, and m1+m2+m3+m4+m5+m6 is an integer of from 2 to 200,

j is an integer of from 2 to 10,

B¹⁰ is Q¹⁰[—SiR_(n)L_(3-n)]_(k),

Q¹⁰ is a (k+j) valent linking group,

R is a hydrogen atom or a monovalent hydrocarbon group,

L is a hydrolyzable group or a hydroxy group,

n is an integer of from 0 to 2, and

k is an integer of from 1 to 10.

-   [10] The fluorinated ether compound according to [9], wherein in the    formula (10), A¹⁰ is a C₁₋₂₀ perfluoroalkyl group, and all the    (R^(f5)O) and (R^(f6)O) are located on the A¹⁰-O— side from the    [0.5×(m1+m2+m3+m4+m5+m6)]th unit as counted from the A¹⁰-O— side.-   [11] A fluorinated ether composition, comprising at least one type    of the fluorinated ether compound as defined in any one of the above    [1] to [10], and another fluorinated ether compound.-   [12] A coating liquid comprising the fluorinated ether compound as    defined in any one of the above [1] to [10] or the fluorinated ether    composition as defined in [11], and a liquid medium.-   [13] An article having a surface layer formed of the fluorinated    ether compound as defined in any one of the above [1] to [10] or the    fluorinated ether composition as defined in [11], on a surface of a    substrate.-   [14] A method for producing an article, which comprises treating a    surface of a substrate by dry coating method using the fluorinated    ether compound as defined in any one of the above [1] to [10] or the    fluorinated ether composition as defined in [11] to form a surface    layer on the surface of the substrate.-   [15] A method for producing an article, which comprises applying the    coating liquid as defined in [12] by wet coating method to a surface    of a substrate, and removing the liquid medium, to form a surface    layer on the surface of the substrate.

The present invention further provides a fluorinated ether compoundrepresented by the following formula (12), a fluorinated ether compoundrepresented by the following formula (13), a fluorinated ether compoundrepresented by the following formula (14) and a fluorinated ethercompound represented by the following compound (15), useful as anintermediate for producing the fluorinated ether compound.A²-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B²  (12)A³-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B³  (13)A⁴-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B⁴  (14)A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B⁵  (15)wherein A² is a C₁₋₂₀ perfluoroalkyl group or B², B² is —R^(f7)—C(O)OR⁸,and R⁸ is a hydrogen atom or a monovalent organic group,

A³ is a C₁₋₂₀ perfluoroalkyl group or B³, and B³ is —R^(f7)—CH₂OH,

A⁴ is a C₁₋₂₀ perfluoroalkyl group or B⁴, and B⁴ is —R^(f7)—I, and

A⁵ is a C₁₋₂₀ perfluoroalkyl group or B⁵, B⁵ is -Q^(a)[-CH═CH₂]_(k) andQ^(a) is a (k+1) valent linking group,

in the formulae (12) to (15),

R^(f1) is a C₁ perfluoroalkylene group, R^(f2) is a C₂ perfluoroalkylenegroup, R^(f3) is a C₃ perfluoroalkylene group, R^(f4) is a C₄perfluoroalkylene group, R^(f5) is a C₅ perfluoroalkylene group, R^(f6)is a C₆ perfluoroalkylene group, and R^(f7) is a C₁₋₆ perfluoroalkylenegroup, and

m1, m2, m3, m4, m5 and m6 are each 0 or an integer of at least 1,m1+m2+m3+m4 is an integer of at least 1, m5+m6 is an integer of at least1, and m1+m2+m3+m4+m5+m6 is an integer of from 2 to 200.

Further, -Q^(a)[—CH═CH₂]_(k) as B⁵ in the formula (5) is preferably agroup represented by any one of the following formulae (g11) to (g16).R^(f7) in the following formula is the same group as R^(f7) in theformulae (12) to (14).—R^(f7)—(X¹)_(p)-Q^(1a)-CH═CH₂  (g11)—R^(f7)—(X²)_(r)-Q²¹-N[-Q^(22a)-CH═CH₂]₂  (g12)—R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-(O)_(t)—C[—(O)^(u)-Q^(32a)-CH═CH₂]₃  (g13)—R^(f7)-Q⁴¹-Si[-Q^(42a)-CH═CH₂]₃  (g14)—R^(f7)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q^(52a)-CH═CH₂]_(w)  (g15)—R^(f7)-Q⁷¹-G(R⁷)[-Q^(72a)-CH═CH₂]₂  (g16)

in the formula (g11),

X¹ is an etheric oxygen atom or —C(O)N(R¹)— (provided that N is bondedto Q^(1a)),

R¹ is a hydrogen atom or an alkyl group,

p is 0 or 1, and

Q^(1a) is an alkylene group, a group having an etheric oxygen atom or asilphenylene skeleton between carbon atoms of an alkylene group havingat least 2 carbon atoms, or a group having a bivalent organopolysiloxaneresidue or a dialkylsilylene group between carbon atoms or at a terminalon the side bonded to (X¹)_(p) of an alkylene group having at least 2carbon atoms,

in the formula (g12),

X² is an etheric oxygen atom, —NH— or —C(O)N(R²)— (provided that N isbonded to Q²¹),

R² is a hydrogen atom or an alkyl group,

r is 0 or 1 (provided that it is 0 when Q²¹ is a single bond),

Q²¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom, —NH—, —C(O)—, —C(O)O— or —OC(O)— between carbon atoms of analkylene group having at least 2 carbon atoms,

Q^(22a) is an alkylene group, or a group having an etheric oxygen atom,—NH— or a bivalent organopolysiloxane residue between carbon atoms of analkylene group having at least 2 carbon atoms, and

two [-Q^(22a)-CH═CH₂] may be the same or different,

in the formula (g13),

R³¹ is a hydrogen atom or an alkyl group,

s is 0 or 1,

Q³¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

t is 0 or 1 (provided that it is 0 when Q³¹ is a single bond),

u is 0 or 1,

Q^(32a) is an alkylene group, a group having an etheric oxygen atom or asilphenylene skeleton between carbon atoms of an alkylene group havingat least 2 carbon atoms, or a group having —C(O)N(R³²)—, a bivalentorganopolysiloxane residue or a dialkylsilylene group between carbonatoms or at a terminal on the side bonded to (O)_(u) of an alkylenegroup having at least 2 carbon atoms,

R³² is a hydrogen atom or an alkyl group, and

three [—(O)_(u)-Q^(32a)-CH═CH₂] may be the same or different,

in the formula (g14),

Q⁴¹ is an alkylene group, or a group having an etheric oxygen atombetween carbon atoms of an alkylene group having at least 2 carbonatoms,

Q⁴²a is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms, and

three [-Q^(42a)-CH═CH₂] may be the same or different,

in the formula (g15),

R⁵ is a hydrogen atom or an alkyl group,

v is 0 or 1,

Q⁵¹ is an alkylene group, or a group having an etheric oxygen atombetween carbon atoms of an alkylene group having at least 2 carbonatoms,

Z is a (w+1) valent organopolysiloxane residue,

Q^(52a) is an alkylene group, or a group having an etheric oxygen atomor a bivalent organopolysiloxane residue between carbon atoms of analkylene group having at least 2 carbon atoms,

w is an integer of from 2 to 7, and

w [-Q^(52a)-CH═CH₂] may be the same or different, in the formula (g16),

Q⁶¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

G is a carbon atom or a silicon atom,

R⁶ is a hydroxy group or an alkyl group,

Q^(62a) is an alkylene group, or a group having an etheric oxygen atomor a bivalent organopolysiloxane residue between carbon atoms of analkylene group having at least 2 carbon atoms, and

two [-Q^(62a)-CH═CH₂] may be the same or different.

Advantageous Effects of Invention

By the fluorinated ether compound of the present invention, it ispossible to form a surface layer excellent in initial water/oilrepellency, fingerprint stain removability, abrasion resistance andlight resistance.

By the fluorinated ether composition of the present invention, it ispossible to form a surface layer excellent in initial water/oilrepellency, fingerprint stain removability, abrasion resistance andlight resistance.

By the coating liquid of the present invention, it is possible to form asurface layer excellent in initial water/oil repellency, fingerprintstain removability, abrasion resistance and light resistance.

The article of the present invention has a surface layer excellent ininitial water/oil repellency, fingerprint stain removability, abrasionresistance and light resistance.

According to the method for producing an article of the presentinvention, it is possible to produce an article having a surface layerexcellent in initial water/oil repellency, fingerprint stainremovability, abrasion resistance and light resistance.

DESCRIPTION OF EMBODIMENTS

In this specification, a compound represented by the formula (1) will bereferred to as compound (1). Compounds represented by other formulaewill be referred to in the same manner.

Further, a group represented by the formula (g1) will be referred to asgroup (g1). Groups represented by other formulae will be referred to inthe same manner.

In this specification, meanings of the following terms and manner ofdescription of chemical formulae are as follows.

A chemical formula of an oxyperfluoroalkylene unit shall be representedso that its oxygen atom be on the right-hand side of theperfluoroalkylene group.

A poly(oxyperfluoroalkylene) chain having units (α) and (β) (hereinaftersometimes referred to as “chain (αβ)”) is a linear bivalent group,wherein one of the two terminals is a connecting bond bonded to a carbonatom (the carbon atom having this connecting bond will be referred to asa terminal carbon atom) and the other is a connecting bond of an oxygenatom (the oxygen atom having this connecting bond will be referred to asa terminal oxygen atom). A chemical formula of the chain (αβ) shall alsobe presented so that the terminal oxygen atom be on the right-hand side.

An “etheric oxygen atom” means an oxygen atom forming an ether bond(—O—) between carbon atoms.

A “hydrolyzable silyl group” means a group capable of forming a silanolgroup (Si—OH) by being hydrolyzed. For example, it may be SiR_(n)L_(3-n)in the formula (1).

A “surface layer” means a layer formed on the surface of a substrate.

The “number average molecular weight” of the fluorinated ether compoundis calculated by obtaining the number (average value) ofoxyperfluoroalkylene groups based on the terminal group as a standard,by ¹H-NMR and ¹⁹F-NMR. The terminal group may, for example, be aperfluoroalkyl group as A¹ or SiR_(n)L_(3-n) as B¹ in the formula (1).

[Fluorinated Ether Compound]

The fluorinated ether compound of the present invention (hereinaftersometimes referred to as “the present compound”) is a compound having apoly(oxyperfluoroalkylene) chain having a unit (α) which is anoxyperfluoroalkylene unit having 5 or 6 carbon atoms and a unit (β)which is an oxyperfluoroalkylene unit having at most 4 carbon atoms,that is, a chain (αβ), and having at least one of a hydrolyzable silylgroup and a silanol group on at least one terminal of the chain (αβ) viaa linking group (hereinafter a hydrolyzable silyl group and a silanolgroup will generally be referred to as a “hydrolyzable silyl group orthe like”).

The number of the chain (αβ) in the present compound may be one, or twoor more. In order to obtain sufficient effects of the present invention,it is preferably one. In a case where the present compound has two ormore chains (αβ), the present compound may be a compound having at leasttwo chains (αβ) connected in series via a bivalent linking group, may bea compound having at least two chains (αβ) branched from a terminal ofone chain (αβ) via a trivalent or higher linking group as a branch, ormay be a compound having at least two chains (αβ) connected in seriesvia a bivalent linking group, and having at least two chains (αβ)branched from a terminal of one chain (αβ) via a trivalent or higherlinking group as a branch.

The number of the hydrolyzable silyl group in the present compound maybe one, or may be two or more. In order to obtain sufficient effects ofthe present invention, it is preferably two or more.

In a case where the number of the chain (αβ) of the present compound isone, the present compound may have a hydrolyzable silyl group or thelike on one terminal of the chain (αβ) via a linking group, or may havea hydrolyzable silyl group or the like on both terminals of the chain(αβ) via a linking group.

The present compound preferably has a hydrolyzable silyl group or thelike only on one terminal of the chain (αβ), in order that the surfacelayer is more excellent in abrasion resistance.

In a case where the present compound has no hydrolyzable silyl group orthe like on one terminal of the chain (αβ) via a linking group, it has amonovalent organic group on that terminal.

In a case where the number of the chain (αβ) of the present compound isone, the present compound is, in order that the surface layer is moreexcellent in initial water/oil repellency, abrasion resistance andfingerprint stain removability, a compound having a C₁₋₂₀ perfluoroalkylgroup bonded to a carbon atom of one end of the chain (αβ) via an oxygenatom and having a hydrolyzable silyl group bonded to an oxygen atom ofthe other end of the chain (αβ) via a linking group.

(Chain (αβ))

The chain (αβ) preferably constitutes a molecular chain having unitsconnected linearly or in branched between a terminal group and a linkinggroup or between linking groups, in order to sufficiently obtain theeffects of the present invention.

The chain (αβ) may have an oxyalkylene unit other than the units (α) and(β). As other unit, an oxypolyfluoroalkylene unit having at least onehydrogen atom may, for example, be mentioned. The chain (αβ) preferablyconsists solely of the unit (α) and the unit (β).

In the chain (αβ), as the unit (α), only one type of the unit (α) may bepresent, or two types of the units (α) differing in the number of carbonatoms may be present.

In the chain (αβ), as the unit (β), only one type of the unit (β) may bepresent, or two or more types of the units (13) differing in the numberof carbon atoms may be present.

In the unit (α), the perfluoroalkylene group may be linear or branched.The unit (α) is, in view of more excellent initial water/oil repellency,abrasion resistance and light resistance of the surface layer,preferably linear, that is, (CF₂CF₂CF₂CF₂CF₂O) or (CF₂CF₂CF₂CF₂CF₂CF₂O).

The unit (β) is, in view of more excellent fingerprint stainremovability of the surface layer, preferably a linearoxyperfluoroalkylene unit, more preferably (CF₂O) or (CF₂CF₂O), and inview of more excellent lubricity of the surface layer, particularlypreferably (CF₂O).

By the chain (αβ) having the unit (α), the surface layer is excellent ininitial water/oil repellency, abrasion resistance and light resistance.However, if it consists only of the unit (α), the crystallinity of thepoly(oxyperfluoroalkylene) chain tends to be too high, wherebyfingerprint stain removability will be insufficient. Accordingly, bycontaining the unit (β), the crystallinity of thepoly(oxyperfluoroalkylene) chain is lowered, and the initial water/oilrepellency, abrasion resistance, fingerprint stain removability andlight resistance of the surface layer can be achieved in a well-balancedmanner.

In the chain (αβ), the proportion of the unit (α) (that is, the numberof the unit (α)/the number of the unit (α) and the number of the unit(β)) is preferably from 0.02 to 0.5, particularly preferably from 0.02to 0.2. That is, in the formula (11) or the like described hereinafter,(m5+m6)/(m1+m2+m3+m4+m5+m6) is preferably from 0.02 to 0.5, particularlypreferably from 0.02 to 0.2. Within such a range, initial water/oilrepellency, abrasion resistance, fingerprint stain removability andlight resistance on the surface layer can be achieved in a well-balancedmanner.

Particularly in the formula (11) or the like, it is preferred that A¹ orthe like is a C₁₋₂₀ perfluoroalkyl group, and the positions of all(R^(f5)O) and (R^(f6)O) are on the A¹-O— side from[0.5×(m1+m2+m3+m4+m5+m6)]th unit as counted from the A¹-O— side. Thatis, they are preferably between the first and[0.5×(m1+m2+m3+m4+m5+m6)]th units as counted from the A¹-O— side.However, in a case where m1+m2+m3+m4+m5+m6 is an odd number, itcorresponds to a natural number not exceeding 0.5 times that number.

In the chain (αβ), the binding order of the unit (α) and the unit (β) isnot limited, and the units may be arranged randomly, in blocks oralternately. In order to efficiently obtain the initial water/oilrepellency, abrasion resistance, fingerprint stain removability andlight resistance on the surface layer, the chain preferably contains astructure having the unit (α) and the unit (β) alternately arranged.

(Linking Group)

The linking group may be a known linking group connecting apoly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group or thelike in a known fluorinated ether compound used as a surface treatmentagent. Of the known linking group, the structure may be changed within arange not to impair the effects of the present invention. The linkinggroup may be properly determined within a range of knowledge of thoseskilled in the art.

(Terminal Group)

The hydrolyzable silyl group or the like is preferably a hydrolyzablesilyl group in view of excellent storage stability of the presentcompound.

The number of the hydrolyzable silyl group or the like bonded to thelinking group is, in order to sufficiently obtain the effects of thepresent invention, preferably from 1 to 10, more preferably from 1 to 3,particularly preferably 2 or 3.

In a case where the present compound has no hydrolyzable silyl group orthe like on one terminal of the chain (αβ) via the linking group, themonovalent organic group present on the terminal is preferably aperfluoroalkyl group or a perfluoroalkyl group having an etheric oxygenatom, particularly preferably a perfluoroalkyl group.

(Present Compound)

The present compound may be a single compound, or may be a mixture oftwo or more types differing in the chain (αβ), the terminal group, thelinking group or the like.

The number average molecular weight of the present compound ispreferably from 2,000 to 10,000. When the number average molecularweight is within such a range, the surface layer is more excellent inthe abrasion resistance. The number average molecular weight of thepresent compound is preferably from 2,100 to 9,000, particularlypreferably from 2,400 to 8,000.

The present compound, which has the chain (αβ), a high content offluorine atoms. Further, as described above, it has the chain (αβ)having the unit (α) to impart high initial water/oil repellency,abrasion resistance and light resistance to the surface layer and theunit (β) to lower the crystallinity of the poly(oxyperfluoroalkylene)chain which is increased by the unit (α). Accordingly, the presentcompound is capable of forming a surface layer having high initialwater/oil repellency and being excellent in abrasion resistance,fingerprint stain removability and light resistance.

By the surface treatment by the present compound, the fluorinated ethercomposition or the coating liquid, as described hereinafter, thehydrolyzable silyl group (SiR_(n)L_(3-n)) in the present compoundundergoes hydrolysis to form a silanol group (Si—OH), such silanolgroups are intermolecularly reacted to form a Si—O—Si bond, or such asilanol group undergoes dehydration condensation with a hydroxy group(substrate —OH) on the surface of the substrate to form a chemical bond(substrate —O—Si). That is, the surface layer in the present inventioncontains the present compound in such a state that some or all ofhydrolyzable silyl groups in the present compound are hydrolyzed andsubjected to dehydration condensation.

(Compound (1))

The present compound is, in order to sufficiently obtain the effects ofthe present invention, preferably compound (1).A¹-O—(R^(f)O)_(m)—B¹  (1)wherein A¹ is a C₁₋₂₀ perfluoroalkyl group or B¹, R^(f) is a C₁₋₆perfluoroalkylene group, m is an integer of from 2 to 200, (R^(f)O)_(m)has the unit (α) and the unit (β), B¹ is -Q[-SiR_(n)L_(3-n)]_(k), Q is a(k+1) valent linking group, R is a hydrogen atom or a monovalenthydrocarbon group, L is a hydrolyzable group or a hydroxy group, n is aninteger of from 0 to 2, and k is an integer of from 1 to 10.<Chain (αβ)>

In the chain (αβ), that is, (R^(f)O)_(m), the bonding order of the unit(α) and the unit (β) is not limited, and the units may be arrangedrandomly, in blocks or alternately. In order to efficiently achieve theinitial water/oil repellency, abrasion resistance, fingerprint stainremovability and light resistance of the surface layer, the chainpreferably contains a structure having the unit (α) and the unit (β)alternately arranged.

The chain (αβ) is, in view of more excellent initial water/oilrepellency, abrasion resistance, fingerprint stain removability andlight resistance of the surface layer, preferably one having at leastone of (CF₂CF₂CF₂CF₂CF₂O) and (CF₂CF₂CF₂CF₂CF₂CF₂O) and at least one of(CF₂O) and (CF₂CF₂O).

The chain (αβ) is preferably one having the following structure in atleast part of the chain (αβ). In the following structural formulae, astructural formula having x1 pieces of unit (α) and x2 pieces of theunit (β) represents a structure having x1 pieces of the unit (α) and x2pieces of the unit (β) arranged randomly or in blocks, and a structurehaving x3 pieces of assembly having the unit (α) and the unit (β) bondedrepresents a structure having the unit (α) and the unit (β) alternatelyarranged. In a structure having the units alternately arranged, if thetotal number of the unit (α) and the unit (β) is an odd number, thechain (αβ) has a structure having (X3-1) pieces of assembly and havingone unit (β) on the terminal on the unit (α) side, or a structure having(X3-1) pieces of assembly and one unit (α) on the terminal on the unit(β) side.

(CF₂CF₂CF₂CF₂CF₂O)_(x1)(CF₂O)_(x2)

(CF₂CF₂CF₂CF₂CF₂O)_(x1)(CF₂CF₂O)_(x2)

(CF₂CF₂CF₂CF₂CF₂CF₂O)_(x1)(CF₂O)_(x2)

(CF₂CF₂CF₂CF₂CF₂CF₂O)_(x1)(CF₂CF₂O)_(x2)

(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)

(CF₂CF₂CF₂CF₂CF₂O—CF₂CF₂O)_(x3)

(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)

(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂CF₂O)_(x3)

(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3)

(CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3)

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)

wherein x1 and x2 are each an integer of at least 1, x1+x2 is an integerof from 2 to 200, and x3 is an integer of from 1 to 100.

The chain (αβ) is preferably one having the following structure, in viewof easy production of the compound (1):

(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)

(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂O

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂O

The chain (αβ) is also preferably one having the following structurehaving a combination two or more of arrangements of the unit (α) and theunit (β) randomly, in blocks or alternately. In the following formulae,x21, x22, x31 and x4 are each an integer of at least 1.

(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x31)—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4)—CF₂CF₂O,wherein x31+x4 is an integer of from 2 to 99.

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x31)—(CF₂CF₂O—CF₂CF₂CF₂CF₂O_(x4)—CF₂CF₂O;wherein x31+x4 is an integer of from 2 to 99.

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x31)—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4)—(CF₂O)_(x21)(CF₂CF₂)_(x22);wherein x21+x22+x31×2+x4×2 is an integer of from 6 to 200.

(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x31)—(CF₂O)_(x21)(CF₂CF₂O)_(x22)—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4)—CF₂CF₂O;wherein x21+X22+X31×2+x4×2 is an integer of from 7 to 199.

CF₂O—CF₂CF₂CF₂CF₂CF₂O—CF₂CF₂O—(CF₂O)_(x21)(CF₂CF₂O)_(x22); whereinx21+x22 is an integer of from 2 to 197.

CF₂O—CF₂CF₂CF₂CF₂CF₂O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4)—CF₂CF₂O; wherein x4is an integer of from 1 to 98.

In the compound (1), (R^(f)O)_(m) may be represented also by[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)].That is, the compound (1) may be represented by the following formula(11):A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B¹  (11)

In the above formula, R^(f1) is a C₁ perfluoroalkylene group, R^(f2) isa C₂ perfluoroalkylene group, R^(f3) is a C₃ perfluoroalkylene group,R^(f4) is a C₄ perfluoroalkylene group, R^(f5) is a C⁵ perfluoroalkylenegroup, R^(f6) is a C₆ perfluoroalkylene group, and m1, m2, m3, m4, m5and m6 are each 0 or an integer of at least 1, provided that m1+m2+m3+m4is an integer of at least 1, m5+m6 is an integer of at least 1, andm1+m2+m3+m4+m5+m6 is an integer of from 2 to 200.

In the above formula, each of the units represented by (R^(f1)O),(R^(f2)O), (R^(f3)O) and (R^(f4)O) is the unit (β), and each of theunits represented by (R^(f5)O) and (R^(f6)O) is the unit (α). In theabove formula, m1 to m6 respectively represent the number of units(R^(f1)O) to (R^(f6)O), not the arrangement of the respective units(R^(f1)O) to (R^(f6)O). For example, (R^(f5)O)_(m5) represents that thenumber of (R^(f5)O) is m5, not the block arrangement structure of(R^(f5)O)_(m5). Likewise, the order of description of (R^(f1)O) to(R^(f6)O) does not represent the binding order of the respective units.

As mentioned above, R^(f2) to R^(f6) are each preferably a linearperfluoroalkylene group. That is, it is preferred that R^(f2) is (CF₂)₂,R^(f3) is (CF₂)₃, R^(f4) is (CF₂)₄, R^(f5) is (CF₂)₅ and R^(f6) is(CF₂)₆.

m1+m2+m3+m4 is, in view of more excellent initial water/oil repellencyon the surface layer, preferably an integer of at least 3, particularlypreferably an integer of at least 5. m1+m2+m3+m4 is, in order that thenumber average molecular weight of the compound (1) is not too high,preferably an integer of at most 45, particularly preferably an integerof at most 30.

m3 and m4 are preferably 0, in view of more excellent fingerprint stainremovability of the surface layer.

m5+m6 is, in view of more excellent initial water/oil repellency,abrasion resistance and light resistance of the surface layer,preferably an integer of at least 3, particularly preferably an integerof at least 5. m5+m6 is, in order that the number average molecularweight of the compound (1) is not too high, preferably an integer of atmost 80, particularly preferably an integer of at most 60.

Further, as described above, (m5+m6)/(m1+m2+m3+m4+m5+m6) is preferablyfrom 0.02 to 0.5, particularly preferably from 0.02 to 0.2.

<A¹ Group>

A¹ is a C₁₋₂₀ perfluoroalkyl group or B¹. The perfluoroalkyl group maybe linear or branched. In view of more excellent lubricity and abrasionresistance on the surface layer, it is preferably a C₁₋₁₀ perfluoroalkylgroup, more preferably a C₁₋₆ perfluoroalkyl group, particularlypreferably a C₁₋₃ perfluoroalkyl group.

A¹ may, for example, be CF₃—, CF₃CF₂—, CF₃CF₂CF₂—, CF₃CF₂CF₂CF₂—,CF₃CF₂CF₂CF₂CF₂—, CF₃CF₂CF₂CF₂CF₂CF₂— or CF₃CF(CF₃)—.

A¹ is, in view of more excellent initial water/oil repellency, abrasionresistance, fingerprint stain removability on the surface layer,preferably CF₃—, CF₃CF₂— or CF₃CF₂CF₂—.

<B¹ Group>

The compound (1) has B¹ on one end or on both ends of the chain (αβ),that is, (R^(f)O)_(m). In a case where the compound (1) has two B¹ inone molecule, the two B¹ may be the same or different. As mentionedabove, according to the description of the chemical formula in thepresent invention, when B¹ is described on the left-side of the chemicalformula, B¹ is bonded to the terminal carbon atom of the chain (αβ) viaan oxygen atom, that is, B—O— is bonded to the left-side of the chain(αβ).

B¹ is a group represented by -Q[-SiR_(n)L_(3-n)]_(k), and the compound(1) has a hydrolyzable silyl group or the like represented bySiR_(n)L_(3-n) at the terminal.

Q may be the same linking group in a known fluorinated ether compoundused as a surface treatment agent, and is preferably a group havingSiR_(n)L_(3-n) removed from any one of the after-described groups (g1)to (g7).

The hydrolyzable group as L is a group which becomes a hydroxy group byhydrolysis reaction. That is, the hydrolyzable silyl group at theterminal of the compound (1) becomes a silanol group (Si—OH) byhydrolysis reaction. Silanol groups will further be intermolecularlyreacted to form Si—O—Si bonds. Further, a silanol group will undergodehydration condensation reaction with a hydroxy group (substrate-OH) onthe surface of a substrate, to form a chemical bond (substrate-O—Si).The compound (1), which has a hydrolyzable silyl group or the like atthe terminal, has favorable adhesion to a substrate, has favorableabrasion resistance and is capable of imparting water/oil repellency tothe surface of a substrate.

L may, for example, be an alkoxy group, a halogen atom, an acyl group oran isocyanate group (—NCO). The alkoxy group is preferably a C₁₋₄ alkoxygroup. The halogen atom is preferably a chlorine atom.

L is, in view of easy industrial production, preferably a C₁₋₄ alkoxygroup or a halogen atom. L is, since outgassing during application willbe less, and storage stability of the compound (1) will be excellent,preferably a C₁₋₄ alkoxy group, and in a case where storage stability ofthe compound (1) for a long time is required, particularly preferably anethoxy group, and in a case where the reaction time after coating shouldbe short, particularly preferably a methoxy group.

The monovalent hydrocarbon group as R may, for example, be an alkylgroup, a cycloalkyl group, an alkenyl group or an allyl group.

R is preferably a monovalent hydrocarbon group, particularly preferablya monovalent saturated hydrocarbon group. The number of carbon atoms inthe monovalent saturated hydrocarbon group is preferably from 1 to 6,more preferably from 1 to 3, particularly preferably from 1 to 2.

R is, in view of easy preparation, preferably a C₁₋₆ alkyl group, morepreferably a C₁₋₃ alkyl group, particularly preferably a C₁₋₂ alkylgroup.

n is preferably 0 or 1, particularly preferably 0. By the presence of aplurality of L in the molecule, bonding to the surface of the substratewill be more firm.

When n is at most 1, the plurality of L present in one molecule may bethe same or different. In view of availability of raw materials andproduction efficiency, they are preferably the same.

The hydrolyzable silyl group (SiR_(n)L_(3-n)) is preferably —Si(OCH₃)₃,—SiCH₃(OCH₃)₂, —Si(OCH₂CH₃)₃, —SiCl₃, —Si(OC(O)CH₃)₃ or —Si(NCO)₃. Inview of handling efficiency in industrial production, —Si(OCH₃)₃ isparticularly preferred.

Further, B¹, that is, the group represented by -Q[-SiR_(n)L_(3-n)]_(k),is preferably a group represented by any one of the formulae (g1) to(g7).—R^(f7)—(X¹)_(p)-Q¹-SiR_(n)L_(3-n)  (g1)—R^(f7)—(X²)_(r)-Q²¹-N[-Q²²-SiR_(n)L_(3-n)]₂  (g2)—R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-(O)_(t)—C[—(O)_(u)-Q³²-SiR_(n)L_(3-n)]₃  (g3)—R^(f7)-Q⁴¹-Si[-Q⁴²-SiR_(n)L_(3-n)]₃  (g4)—R^(f7)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q⁵²-SiR_(n)L_(3-n)]_(w)  (g5)—R^(f7)-Q⁶¹-G(R⁶)[-Q⁶²-SiR_(n)L_(3-n)]₂  (g6)—R^(f7)-Q⁷¹-[CH₂C(R⁷¹)(-Q⁷²-SiR_(n)L_(3-n))]_(y)-R⁷²  (g7)

wherein R^(f7) is a C₁₋₆ perfluoroalkylene group,

R is a hydrogen atom or a monovalent hydrocarbon group,

L is a hydrolyzable group or a hydroxy group, and

n is an integer of from 0 to 2.

In the formula (g1),

X¹ is an etheric oxygen atom or —C(O)N(R¹)— (provided that N is bondedto Q¹),

R¹ is a hydrogen atom or an alkyl group,

p is 0 or 1, and

Q¹ is an alkylene group, a group having an etheric oxygen atom or asilphenylene skeleton between carbon atoms of an alkylene group havingat least 2 carbon atoms, or a group having a bivalent organopolysiloxaneresidue or a dialkylsilylene group between carbon atoms or at a terminalon the side bonded to (X¹)_(p) of an alkylene group having at least 2carbon atoms.

In the formula (g2),

X² is an etheric oxygen atom, —NH— or —C(O)N(R²)— (provided that N isbonded to Q²¹),

R² is a hydrogen atom or an alkyl group,

r is 0 or 1 (provided that it is 0 when Q²¹ is a single bond),

Q²¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom, —NH—, —C(O)—, —C(O)O— or —OC(O)— between carbon atoms of analkylene group having at least 2 carbon atoms,

Q²² is an alkylene group, or a group having an etheric oxygen atom, —NH—or a bivalent organopolysiloxane residue between carbon atoms of analkylene group having at least 2 carbon atoms, and

two [-Q²²-SiR_(n)L_(3-n)] may be the same or different.

In the formula (g3),

R³¹ is a hydrogen atom or an alkyl group,

s is 0 or 1,

Q³¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

t is 0 or 1 (provided that it is 0 when Q³¹ is a single bond),

u is 0 or 1,

Q³² is an alkylene group, a group having an etheric oxygen atom or asilphenylene skeleton between carbon atoms of an alkylene group havingat least 2 carbon atoms, or a group having —C(O)N(R³²)—, a bivalentorganopolysiloxane residue or a dialkylsilylene group between carbonatoms or at a terminal on the side bonded to (O)_(u) of an alkylenegroup having at least 2 carbon atoms,

R³² is a hydrogen atom or an alkyl group, and

three [—(O)_(u)-Q³²-SiR_(n)L_(3-n)] may be the same or different.

In the formula (g4),

Q⁴¹ is an alkylene group, or a group having an etheric oxygen atombetween carbon atoms of an alkylene group having at least 2 carbonatoms,

Q⁴² is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms, and

three [-Q⁴²-SiR_(n)L_(3-n)] may be the same or different.

In the formula (g5),

R⁵ is a hydrogen atom or an alkyl group,

v is 0 or 1,

Q⁵¹ is an alkylene group, or a group having an etheric oxygen atombetween carbon atoms of an alkylene group having at least 2 carbonatoms,

Z is a (w+1) valent organopolysiloxane residue,

Q⁵² is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms,

w is an integer of from 2 to 7, and

w [-Q⁵²-SiR_(n)L_(3-n)] may be the same or different.

In the formula (g6),

Q⁶¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

G is a carbon atom or a silicon atom,

R⁶ is a hydroxy group or an alkyl group,

Q⁶² is an alkylene group, or a group having an etheric oxygen atom or abivalent organopolysiloxane residue between carbon atoms of an alkylenegroup having at least 2 carbon atoms, and

two [-Q⁶²-SiR_(n)L_(3-n)] may be the same or different.

In the formula (g7),

Q⁷¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms,

R⁷¹ is a hydrogen atom or an alkyl group,

Q⁷² is a single bond or an alkylene group,

R⁷² is a hydrogen atom or a halogen atom,

y is an integer of from 1 to 10, and

two to ten [-Q⁷²-SiR_(n)L_(3-n)] may be the same or different.

B¹ is, so as to more sufficiently achieve the effects of the presentinvention, particularly preferably the group (g2), the group (g3), thegroup (g4), the group (g5) or the group (g6).

Hereinafter, with respect to the compound (1) represented by the formula(11), a compound (1) wherein B¹ is the group (g1) will be referred ascompound (11a), a compound (1) wherein B¹ is the group (g2) as compound(11b), a compound (1) wherein B¹ is the group (g3) as compound (11c), acompound (1) wherein B¹ is the group (g4) as compound (11d), a compound(1) wherein B¹ is the group (g5) as compound (11e), a compound (1)wherein B¹ is the group (g6) as compound (11f), and a compound (1)wherein B¹ is the group (g7) as compound (11g).A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—(X¹)_(p)-Q¹-SiR_(n)L_(3-n)  (11a),A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—(X²)_(r)-Q²¹-N[-Q²²-SiR_(n)L_(3-n)]₂  (11b),A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-(O)_(t)—C[—(O)_(u)-Q³²-SiR_(n)L_(3-n)]₃  (11c),A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)-Q⁴¹-Si[-Q⁴²-SiR_(n)L_(3-n)]₃  (11d),A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q⁵²-SiR_(n)L_(3-n)]_(w)  (11e),A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)-Q⁶¹-G(R⁶)[-Q⁶²-SiR_(n)L_(3- n)]₂  (11f).A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)-Q⁷¹-[CH₂C(R⁷¹)(-Q⁷²-SiR_(n)L_(3-n))]_(y)-R⁷²  (11g).

R^(f7) may be linear or branched. R^(f7) is, in order that the compound(1) is easily produced, preferably —CF₂CF₂CF₂CF₂— or —CF₂CF₂CF₂CF₂CF₂—.

Preferred embodiments of R, L, n and SiR_(n)L_(3-n) are the same as thepreferred embodiments of SiR_(n)L_(3-n) in the compound (1).

As the bivalent organopolysiloxane residue in each of the groups (g1) to(g6), the following groups may be mentioned. In the following formulae,R^(a) is a hydrogen atom, an alkyl group, an alkoxy group or a phenylgroup. The number of carbon atoms in the alkyl group or the alkoxy groupin R^(a) is preferably from 1 to 10, particularly preferably 1.

The silphenylene skeleton in the group (g1) or the group (g3) is a grouprepresented by —Si(R^(b))₂PhSi(R^(b))₂— (wherein Ph is a phenylenegroup, and R^(b) is a monovalent organic group). R^(b) is preferably aC₁₋₁₀ alkyl group, particularly preferably a methyl group.

The dialkylsilylene group in the group (g1) or the group (g3) is a grouprepresented by —Si(R^(c))₂— (wherein R^(c) is an alkyl group). R^(c) ispreferably a C₁₋₁₀ alkyl group, particularly preferably a methyl group.

<Compound (11a)>

R¹ is preferably a hydrogen atom or a C₁₋₄ alkyl group, and in view ofeasy production of the compound (11a), preferably a hydrogen atom.

Q¹ is preferably a C₁₋₁₀ alkylene group, a group having an ethericoxygen atom or a silphenylene skeleton between carbon atoms of a C₂₋₁₀alkylene group, or a group having a bivalent organopolysiloxane residueor a dialkylsilylene group between carbon atoms or at a terminal on theside bonded to (X¹)_(p) of a C₂₋₁₀ alkylene group. Q¹ is, in view ofeasy production of the compound (11a), in a case where (X¹)_(p) is asingle bond, preferably —CH₂OCH₂CH₂CH₂—, —CH₂OCH₂CH₂OCH₂CH₂CH₂—,—CH₂CH₂—, —CH₂CH₂CH₂— or —CH₂OCH₂CH₂CH₂Si(CH₃)₂OSi(CH₃)₂CH₂CH₂—, in acase where (X¹)_(p) is —O—, preferably —CH₂CH₂CH₂— or—CH₂CH₂OCH₂CH₂CH₂—, and in a case where (X¹)_(p) is —C(O)N(R¹)—,preferably a C₂₋₆ alkylene group (provided that the right side is bondedto Si).

As specific examples of the compound (11a), the following compounds maybe mentioned. Here, in a case where a perfluoropolyether chain, that is,the chain (αβ) has B¹ on one end, PFPE isA¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—and in a case where the chain (αβ) has B¹ on both ends, PFPE is—R^(f7)—O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—.A preferred embodiment of PFPE is a combination of the above preferredA¹, chain (αβ) and R^(f7).

<Compound (11b)>

(X²)_(r) is, in view of easy production of compound (11b), preferably asingle bond.

R² is preferably a hydrogen atom or a C₁₋₄ alkyl group, and in view ofeasy production of compound (11b), preferably a hydrogen atom.

Q²¹ is, in a case where (X²)_(r) is a single bond, preferably a C₁₋₁₀alkylene group or a group having an etheric oxygen atom or —NH— betweencarbon atoms of a C₂₋₁₀ alkylene group, and in view of easy productionof the compound (11b), particularly preferably —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂OCH₂CH₂— or —CH₂NHCH₂CH₂— (provided that the right sideis bonded to N).

Q²² is preferably a C₁₋₁₀ alkylene group, or a group having an ethericoxygen atom or —NH— between carbon atoms of a C₂₋₁₀ alkylene group, andin view of easy production of the compound (11b), particularlypreferably CH₂CH₂CH₂— or —CH₂CH₂OCH₂CH₂CH₂— (provided that the rightside is bonded to Si).

As specific examples of the compound (11b), the following compounds maybe mentioned. PFPE is the same as the PFPE in the compound (11a), andthe preferred embodiment is also the same.

<Compound (11c)>

R³¹ is, in view of easy production of the compound (11c), preferably ahydrogen atom. The alkyl group as R³¹ is preferably a C₁₋₄ alkyl group.

Q³¹ is preferably a C₁₋₁₀ alkylene group or a group having an ethericoxygen atom between carbon atoms of a C₂₋₁₀ alkylene group. -Q³¹-O)_(t)—is, in view of easy production of the compound (11c), in a case where sis 0, preferably a single bond, —CH₂O—, —CH₂OCH₂—, —CH₂OCH₂CH₂O— or—CH₂OCH₂CH₂OCH₂— (provided that the left side is bonded to R^(f7)), andin a case where s is 1, preferably a single bond or —CH₂—, —CH₂CH₂—.

R³² is preferably a hydrogen atom or a C₁₋₄ alkyl group, and in view ofeasy production of the compound (11c), preferably a hydrogen atom.

Q³² is preferably a C₁₋₁₀ alkylene group, a group having an ethericoxygen atom or a silphenylene skeleton between carbon atoms of a C₂₋₁₀alkylene group, or a group having —C(O)N(R³²)—, a bivalentorganopolysiloxane residue or a dialkylsilylene group between carbonatoms or at a terminal on the side bonded to (O)_(u) of a C₂₋₁₀ alkylenegroup. —(O)_(u)-Q³²- is, in view of easy production of the compound(11c), preferably —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂OCH₂CH₂CH₂—,—CH₂OCH₂CH₂CH₂CH₂CH₂—, —OCH₂CH₂CH₂—, —OSi(CH₃)₂CH₂CH₂CH₂—,—OSi(CH₃)₂OSi(CH₃)₂CH₂CH₂CH₂— or —CH₂CH₂CH₂Si(CH₃)₂PhSi(CH₃)₂CH₂CH₂—(provided that the right side is bonded to Si).

As specific examples of the compound (11c), the following compounds maybe mentioned. PFPE is the same as PFPE in the compound (11a), and thepreferred embodiment is also the same.

<Compound (11d)>

Q⁴¹ is preferably a C₁₋₁₀ alkylene group, or a group having an ethericoxygen atom between carbon atoms of a C₂₋₁₀ alkylene group, and in viewof easy production of the compound (11d), preferably —CH₂OCH₂CH₂CH₂—,—CH₂OCH₂CH₂OCH₂CH₂CH₂—, —CH₂CH₂— or —CH₂CH₂CH₂— (provided that the rightside is bonded to Si).

Q⁴² is preferably a C₁₋₁₀ alkylene group or a group having an ethericoxygen atom or a bivalent organopolysiloxane residue between carbonatoms of a C₂₋₁₀ alkylene group, and in view of easy production of thecompound (11d), preferably —CH₂CH₂CH₂— or —CH₂CH₂OCH₂CH₂CH₂— (providedthat the right side is bonded to SiR_(n)L_(3-n)).

As specific examples of the compound (11d), the following compounds maybe mentioned. PFPE is the same as PFPE in the compound (11a), and thepreferred embodiment is also the same.

<Compound (11e)>

R⁵ is preferably a hydrogen atom or a C₁₋₄ alkyl group, and in view ofeasy production of the compound (11e), preferably a hydrogen atom.

Q⁵¹ is preferably a C₁₋₁₀ alkylene group, or a group having an ethericoxygen atom between carbon atoms of a C₂₋₁₀ alkylene group, and in viewof easy production of the compound (11e), preferably —CH₂OCH₂CH₂CH₂—,—CH₂OCH₂CH₂OCH₂CH₂CH₂—, —CH₂CH₂— or —CH₂CH₂CH₂— (provided that the rightside is bonded to Z).

Q⁵² is preferably a C₁₋₁₀ alkylene group or a group having an ethericoxygen atom or a bivalent organopolysiloxane residue between carbonatoms of a C₂₋₁₀ alkylene group, and in view of easy production of thecompound (11e), preferably —CH₂CH₂— or —CH₂CH₂CH₂—.

As the (w+1) valent organopolysiloxane residue as Z, the followinggroups may be mentioned. In the following formulae, R^(a) is a hydrogenatom, an alkyl group, an alkoxy group or a phenyl group. The number ofcarbon atoms of the alkyl group or the alkoxy group as R^(a) ispreferably from 1 to 10, particularly preferably 1.

<Compound (11f)>

Q⁶¹ is preferably a single bond, a C₁₋₁₀ alkylene group, or a grouphaving an etheric oxygen atom between carbon atoms of a C₂₋₁₀ alkylenegroup, and in view of easy production of the compound (11f),particularly preferably a single bond.

G(R⁶) is, in view of easy production of the compound (11f), preferablyC(OH) or Si(R^(6a)) (wherein R^(6a) is an alkyl group, the number ofcarbon atoms of which is preferably from 1 to 10, particularlypreferably 1).

Q⁶² is preferably a C₁₋₁₀ alkylene group, or a group having an ethericoxygen atom between carbon atoms of a C₂₋₁₀ alkylene group, and in viewof easy production of the compound (11f), preferably —CH₂CH₂—,—CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—.

As specific examples of the compound (11f), the following compounds maybe mentioned. PFPE is the same as the PFPE in the compound (11a), andthe preferred embodiment is also the same.

<Compound (11g)>

Q⁷¹ is preferably a single bond, a C₁₋₁₀ alkylene group or a grouphaving an etheric oxygen atom between carbon atoms of a C₂₋₁₀ alkylenegroup, and in view of easy production of the compound (11g), preferablya single bond.

R⁷¹ is preferably a hydrogen atom or a C₁₋₁₀ alkyl group, and in view ofeasy production of the compound (11g), preferably a hydrogen atom. Thealkyl group as R⁷¹ is preferably a methyl group.

Q⁷² is a single bond or a C₁₋₁₀ alkylene group, and in view of easyproduction of the compound (11g), preferably a single bond or —CH₂—.

R⁷² is, in view of easy production of the compound (11g), preferably ahydrogen atom.

As specific examples of the compound (11g), the following compounds maybe mentioned. PFPE is the same as the PFPE in the compound (11a), andthe preferred embodiment is also the same.

(Compound (10))

The present compound other than the compound (1) is, in order to achievethe effects of the present invention, preferably compound (10)represented by the following formula (10). The compound (10) is acompound having at least 2 chains (αβ), whereas the compound (1)represented by the formula (1) or the formula (11) is a compound havingone chain (αβ).[A¹⁰-O—{(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5))_(m5)(R^(f6)O)_(m6)}]_(j)—B¹⁰  (10)wherein A¹⁰ is a C₁₋₂₀ perfluoroalkyl group or B¹⁰, R^(f1) to R^(f6) arethe same as R^(f1) to R^(f6) in the above formula (11), m1 to m6 are thesame as m1 to m6 in the formula (11), j is an integer of from 2 to 10,B¹⁰ is Q¹⁰[-SiR_(n)L_(3-n)]_(k), is a (k+j) valent linking group, R is ahydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzablegroup or a hydroxy group, n is an integer of from 0 to 2, and k is aninteger of from 1 to 10.

The preferred embodiment of the chain (αβ) is the same as the preferredembodiment of the chain (αβ) in the compound (1).

The preferred embodiment of the C₁₋₂₀ perfluoroalkyl group as A¹⁰ is thesame as the preferred embodiment of the C₁₋₂₀ perfluoroalkyl group as A¹in the compound (1).

The compound (10) has from one to (1+j) B¹⁰. In a case where thecompound (10) has a plurality of B¹⁰ in its molecule, they may be thesame or different.

B¹⁰ is a group represented by Q¹⁰[-SiR_(n)L_(3-n)]_(k), and the compound(10) has a hydrolyzable silyl group or the like represented bySiR_(n)L_(3-n) at its terminal. The preferred embodiment ofSiR_(n)L_(3-n) is the same as the preferred embodiment of SiR_(n)L_(3-n)in the compound (1).

Q¹⁰ may be the same as the linking group in a known fluorinated ethercompound used as a surface treatment agent. Q¹⁰ may, for example, bespecifically a group having a (k+j) valent cyclic structure having acarbon atom or a nitrogen atom to which j chains (αβ) are bondeddirectly or via a bivalent linking group, and having a carbon atom or anitrogen atom to which k SiR_(n)L_(3-n) is bonded directly or via abivalent linking group. Such a bivalent linking group may be a singlebond, —C(O)NH— or an alkylene group.

[Method for Producing Fluorinated Ether Compound]

The present compound may be produced in the same manner as the methodfor producing a known fluorinated ether compound used as a surfacetreatment agent, except that a raw material having a specific chain (αβ)or its precursor chain is used as a part of or the entirepolyfluoropolyether chain.

(Method for Producing Compound (1))

In a case where the present compound is the compound (1), the compound(1) may be produced, for example, by the following method.

To a terminal of an ester-terminal fluorinated ether compound (theafter-described compound (2)), a hydroxy group-terminal fluorinatedether compound (the after-described compound (3)) or an iodine-terminalfluorinated ether compound (the after-described compound (4)), acarbon-carbon unsaturated double bond is introduced by a known method toobtain an unsaturated double bond-terminal fluorinated ether compound(the after-described compound (5)), and subjecting the compound (5) andHSiR_(n)L_(3-n) to hydrosilylation reaction to obtain the compound (1).

A method of polymerizing CH₂═CH—SiR_(n)L_(3-n), CH₂═CHCH₂—SiR_(n)L_(3-n)or the like using an iodine-terminal fluorinated ether compound(compound (4)) as an initiator to obtain the compound (1).

<Compound (2)>

The compound (2) is a compound represented by the following formula (2)and may be represented also by the following formula (12). The compoundrepresented by the following formula (12) will hereinafter be referredto as “compound (12)”.A²-O—(R^(f)O)_(m)—B²  (2)A²-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B²  (12)wherein A² is a C₁₋₂₀ perfluoroalkyl group or B², B² is —R^(f7)—C(O)OR⁸,and R⁸ is a hydrogen atom or a monovalent organic group.

The C₁₋₂₀ perfluoroalkyl group as A² is the same as the C₁₋₂₀perfluoroalkyl group as A¹ in the compound (1), and the preferredembodiment is also the same. R^(f7) is the same as R^(f7) in thepreferred B¹ (B¹ represented by the formula (g1) to (g7)) in thecompound (1), and the preferred embodiment is also the same.

R⁸ is preferably an alkyl group. The number of carbon atoms of the alkylgroup is preferably from 1 to 10, particularly preferably 1.

<Compound (3)>

The compound (3) is a compound represented by the following formula (3),and may be represented also by the following formula (13). The compoundrepresented by the following formula (13) will be referred to as“compound (13)”.A³-O—(R^(f)O)_(m)—B³  (3)A³-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B³  (13)wherein A³ is a C₁₋₂₀ perfluoroalkyl group or B³, and B³ is—R^(f7)—CH₂OH.

The C₁₋₂₀ perfluoroalkyl group as A³ is the same as the C₁₋₂₀perfluoroalkyl group as A¹ in the compound (1), and the preferredembodiment is also the same. R^(f7) is the same as R^(f7) in thepreferred B¹ (B¹ represented by the formula (g1) to (g7)) in thecompound (1)), and the preferred embodiment is also the same.

<Compound (4)>

The compound (4) is a compound represented by the following formula (4),and may be represented also by the following formula (14). The compoundrepresented by the following formula (14) will be hereinafter referredto as “compound (14)”.A⁴-O—(R^(f)O)_(m)—B⁴  (4)A⁴-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B⁴  (14)wherein A⁴ is a C₁₋₂₀ perfluoroalkyl group or B⁴, and B⁴ is —R^(f7)—I.

The C₁₋₂₀ perfluoroalkyl group as A⁴ is the same as the C₁₋₂₀perfluoroalkyl group as A¹ in the compound (1), and the preferredembodiment is also the same. R^(f7) is the same as R^(f7) in thepreferred B¹ (B¹ represented by the formula (g1) to (g7)) in thecompound (1), and the preferred embodiment is also the same.

<Compound (5)>

The compound (5) is a compound represented by the following formula (5),and may be represented by the following formula (15). A compoundrepresented by the following formula (15) will be hereinafter referredto as “compound 15”.A⁵-O—(R^(f)O)_(m)—B⁵  (5)A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B⁵  (15)wherein A⁵ is a C₁₋₂₀ perfluoroalkyl group or B⁵, and B⁵ is-Q^(a)[-CH═CH₂]_(k), and Q^(a) is a (k+1) valent linking group.

The C₁₋₂₀ perfluoroalkyl group as A⁵ is the same as the C₁₋₂₀perfluoroalkyl group as A¹ in the compound (1), and the preferredembodiment is also the same. k is the same as k in the compound (1), andthe preferred embodiment is also the same. R^(f7) is the same as R^(f7)in the preferred B¹ (B¹ represented by the formula (g1) to (g7)) in thecompound (1), and the preferred embodiment is also the same.

In the compound (5), B⁵ is preferably a group represented by any one ofthe following formulae (g11) to (g16) corresponding to the groupsrepresented by the formulae (g1) to (g7) in the compound (1).—R^(f7)—(X¹)_(p)-Q^(1a)-CH═CH₂  (g11)—R^(f7)—(X²)_(r)-Q²¹-N[-Q^(22a)-CH═CH₂]₂  (g12)—R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-(O)_(t)—C[—(O)_(u)-Q^(32a)-CH═CH₂]₃  (g13)—R^(f7)-Q⁴¹-Si[-Q^(42a)-CH═CH₂]₃  (g14)—R^(7f)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q^(52a)-CH═CH₂]_(w)  (g15)—R^(f7)-Q⁶¹-G(R⁶)[-Q^(62a)-CH═CH₂]₂  (g16)

In the formula (g11), X¹ and p are the same as X¹ and p in the formula(g1), and the preferred embodiment is also the same. Q^(1a) is analkylene group (preferably a C₁₋₈ alkylene group), a group having anetheric oxygen atom or a silphenylene skeleton between carbon atoms ofan alkylene group having at least 2 (preferably from 2 to 8) carbonatoms, or a group having a bivalent organopolysiloxane residue or adialkylsilylene group between carbon atoms or at a terminal on the sidebonded to (X¹)_(p) of an alkylene group having at least 2 carbon atoms.Q^(1a)-CH═CH₂ constitutes at least a part of Q¹ in the formula (g1)after the after-described hydrosilylation reaction.

In the formula (12), X², R², r and Q²¹ are the same as X², R², r and Q²¹in the formula (g2), and the preferred embodiment is also the same. Q²²ais an alkylene group (preferably a C₁₋₈ alkylene group), or a grouphaving an etheric oxygen atom, —NH— or a bivalent organopolysiloxaneresidue between carbon atoms of an alkylene group having at least 2(preferably from 2 to 8) carbon atoms. Q^(22a)-CH═CH₂ constitutes atleast a part of Q²² in the formula (g2) after the after-describedhydrosilylation reaction. Two [-Q^(22a)-CH═CH₂] may be the same ordifferent.

In the formula (g13), R³¹, s, Q³¹, t, u and R³² are the same as R³¹, s,Q³¹, t, u and R³² in the formula (g3), and the preferred embodiment isalso the same. Q^(32a) is an alkylene group (preferably a C₁₋₈ alkylenegroup), a group having an etheric oxygen atom or a silphenylene skeletonbetween carbon atoms of an alkylene group having at least 2 (preferablyfrom 2 to 8) carbon atoms, or a group having —C(O)N(R³²)—, a bivalentorganopolysiloxane residue or a dialkylsilylene group between carbonatoms or at a terminal on the side bonded to (O)_(u) of an alkylenegroup having at least 2 carbon atoms. Q^(32a)-CH═CH₂ constitutes atleast a part of Q³² in the formula (g3) after the after-describedhydrosilylation reaction. Three [—(O)_(u)-Q^(32a)-CH═CH₂] may be thesame or different.

In the formula (g14), Q⁴¹ is the same as Q⁴¹ in the formula (g4), andthe preferred embodiment is also the same. Q^(42a) is an alkylene group(preferably a C₁₋₈ alkylene group) or a group having an etheric oxygenatom or a bivalent organopolysiloxane residue between carbon atoms of analkylene group having at least 2 (preferably from 2 to 8) carbon atoms.Q^(42a)-CH═CH₂ constitutes at least a part of Q⁴² in the formula (g4)after the after-described hydrosilylation reaction. Three[-Q^(42a)-CH═CH₂] may be the same or different.

In the formula (g15), R⁵, v, Q⁵¹, Z and w are the same as R⁵, v, Q⁵¹ andZ in the formula (g5), and the preferred embodiment is also the same.Q⁵²a is an alkylene group (preferably a C₁₋₈ alkylene group) or a grouphaving an etheric oxygen atom or a bivalent organopolysiloxane residuebetween carbon atoms of an alkylene group having at least 2 (preferablyfrom 2 to 8) carbon atoms. Q^(52a)-CH═CH₂ constitutes at least a part ofQ⁵² in the formula (g5) after the after-described hydrosilylationreaction. w [-Q^(52a)-CH═CH₂] may be the same or different.

In the formula (g16), Q⁶¹, G and R⁶ are the same as Q⁶¹, G and R⁶ in theformula (g6), and the preferred embodiment is also the same. Q^(62a) isan alkylene group (preferably a C₁₋₈ alkylene group) or a group havingan etheric oxygen atom or a bivalent organopolysiloxane residue betweencarbon atoms of an alkylene group having at least 2 (preferably from 2to 8) carbon atoms. Q^(62a)-CH═CH₂ constitutes at least a part of Q⁶² inthe formula (g6) after the after-described hydrosilylation reaction. Two[-Q^(62a)-CH═CH₂] may be the same or different.

Hereinafter, a compound (15) wherein B⁵ is the group (g11) will bereferred to as compound (15a), a compound (15) wherein B⁵ is the group(g12) as compound (15b), a compound (15) wherein B⁵ is the group (g13)as compound (15c), a compound (15) wherein B⁵ is the group (g14) ascompound (15d), a compound (15) wherein B⁵ is the group (g15) ascompound (15e), and a compound (15) wherein B⁵ is the group (g16) ascompound (15f).A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—(X¹)_(p)-Q^(1a)-CH═CH₂  (15a),A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—(X²)₄-Q²¹-N[-Q^(22a)-CH═CH₂]₂  (15b),A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-(O)_(t)—C[—(O)_(u)-Q^(32a)-CH═CH₂]₃  (15c),A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)-Q⁴¹-Si[-Q^(42a)-CH═CH₂]₃  (15d),A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q^(52a)-CH═CH₂]_(w)  (15e),A⁵-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)ma(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—R^(f7)-Q⁶¹-G(R⁶)[-Q^(62a)-CH═CH₂]₂  (15f).

SPECIFIC EXAMPLES OF METHOD FOR PRODUCING EACH COMPOUND

<Method (1) for Producing Compound (12)>

In accordance with the method disclosed in U.S. Pat. No. 4,740,579, inthe presence of an acid, HOCH₂CF₂CF₂CF₂CH₂OH and HC(O)H are reacted toobtain compound (21-1) (1,3-dioxa-5,5,6,6,7,7-hexafluorocyclooctane).

In accordance with the method disclosed in U.S. Pat. No. 4,740,579, inthe presence of an acid and HOCH₂CF₂CF₂CF₂CH₂OH, the compound (21-1) issubjected to ring-opening polymerization to obtain compound (22-1).HOCH₂CF₂CF₂CF₂CH₂O(CH₂OCH₂CF₂CF₂CF₂CH₂O)_(x3)H  (22-1)

The compound (22-1) and an acid halide (for example, R^(f8)C(O)F(wherein R^(f8) is a perfluoroalkyl group or a group having an ethericoxygen atom between carbon atoms of a perfluoroalkyl group having atleast 2 carbon atoms) are reacted for esterification to obtain compound(23-1), which is further fluorinated to obtain compound (24-1).R^(f8)C(O)OCH₂CF₂CF₂CF₂CH₂O(CH₂OCH₂CF₂CF₂CF₂CH₂O)_(x3)C(O)R^(f8)  (23-1)R^(f8)C(O)OCF₂CF₂CF₂CF₂CF₂O(CF₂OCF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8)  (24-1)

Compound (24-2) may be obtained instead of the compound (24-1) by usingHOCH₂CF₂CF₂CF₂CF₂CH₂OH instead of HOCH₂CF₂CF₂CF₂CH₂OH when the compounds(21-1) and (22-1) are obtained.R^(f8)C(O)OCF₂CF₂CF₂CF₂CF₂CF₂O(CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8)  (24-2)

Further, compound (24-3) instead of the compound (24-1), or compound(24-4) instead of the compound (24-2), may be obtained by using a monool(for example, CH₃OH or CF₃CH₂OH) when the compound (22-1) is obtained.R^(f9)O(CF₂OCF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8)  (24-3)R^(f9)O(CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8)  (24-4)wherein R^(f9) is a C₁₋₂₀ perfluoroalkyl group derived from the monool.

Compounds (12-1) to (12-4) are obtained by the reaction of the compounds(24-1) to (24-4) and R⁸OH.R⁸OC(O)CF₂CF₂CF₂CF₂O(CF₂OCF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂F₂C(O)OR⁸  (12-1)R⁸OC(O)CF₂CF₂CF₂CF₂CF₂O(CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂CF₂C(O)OR⁸  (12-2)R^(f9)O(CF₂OCF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂C(O)OR⁸  (12-3)R^(f9)O(CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂CF₂C(O)OR⁸  (12-4)<Method (2) for Producing Compound (12)>

A method to prepare CF₂═CFO(CF₂)₃C(O)CH₃ from HO(CH₂)₄OH is disclosed inJournal of Fluorine Chemistry, vol. 126, 2005, p. 521 to 527. In themethod, by using HO(CH₂)₅OH or HO(CH₂)₆OH instead of HO(CH₂)₄OH,compound (31-1) or compound (31-2) is obtained.CF₂═CFO(CF₂)₄C(O)OCH₃  (31-1)CF₂═CFO(CF₂)₅C(O)OCH₃  (31-2)

The compound (31-1) or (31-2) is subjected to hydrogen reduction byusing a reducing agent (such as sodium borohydride or lithium aluminumhydride) to obtain compound (32-1) or (32-2).CF₂═CFO(CF₂)₄CH₂OH  (32-1)CF₂═CFO(CF₂)₅CH₂OH  (32-2)

Patent Document 1 discloses a method in whichR^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8) is prepared fromCF₂═CFO(CF₂)₃CH₂OH and furtherR^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂C(O)OR⁸ isprepared. In this method, by using the compound (32-1) or (32-2) insteadof CF₂═CFO(CF₂)₃CH₂OH, compound (24-5) or (24-6) and further compound(12-5) or (12-6) are obtained.R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8)  (24-5)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)R^(f8)  (24-6)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂C(O)OR⁸  (12-5)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CF₂C(O)OR⁸  (12-6)<Method for Producing Compound (13)>

The compounds (12-1) to (12-6) are subjected to hydrogen reduction usinga reducing agent to obtain compounds (13-1) to (13-6).HOCH₂CF₂CF₂CF₂CF₂O(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂CH₂OH  (13-1)HOCH₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂CF₂CH₂OH  (13-2)R^(f9)O(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂CH₂OH  (13-3)R^(f9)O(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂CF₂CH₂OH  (13-4)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CH₂OH  (13-5)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CF₂CH₂OH  (13-6)<Method for Producing Compound (14)>

A metal fluoride (such as NaF, CsF, KF or AgF) and the compound (24-1)are reacted to obtain compound (25-1).FC(O)CF₂CF₂CF₂CF₂O(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂C(O)F  (25-1)

The compound (25-1) was iodized using an iodizing agent (such as LiI oriodine/potassium carbonate) to obtain compound (14-1).ICF₂CF₂CF₂CF₂O(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂I  (14-1)

Further, compounds (14-2) to (14-6) may be obtained instead of thecompound (14-1) by using the compounds (24-2) to (24-6) instead of thecompound (24-1).ICF₂CF₂CF₂CF₂CF₂O(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂CF₂I  (14-2)R^(f9)O(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂I  (14-3)R^(f9)O(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(x3)CF₂CF₂CF₂CF₂CF₂I  (14-4)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂I  (14-5)R^(f9)O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CF₂I  (14-6)<Method for Producing Compound (11a)>

The compound (11a) may be produced, for example, in accordance with themethod disclosed in e.g. Patent Document 1 or JP-A-2012-072272, usingthe compound (12-1) to (12-6), the compound (13-1) to (13-6) or thecompound (14-1) to (14-6) as the starting material, via the compound(15a).

<Method for Producing Compound (11b)>

The compound (11b) may be produced, for example, in accordance with themethod disclosed in WO2017/038832, using the compound (13-1) to (13-6)as the starting material, via the compound (15b).

<Method for Producing Compound (11c)>

The compound (11c) shown in paragraph [0061] may be produced, forexample, in accordance with the method disclosed in WO2017/038830, usingthe compound (13-1) to (13-6) as the starting material, via the compound(15c) wherein s=0.

The compound (11c) shown in paragraph [0062] may be produced, forexample, in accordance with the method disclosed in JP-A-2016-204656,using the compound (12-1) to (12-6) as the starting material, via thecompound (15f) wherein G(R⁶) is C(OH).

The compound (11c) shown in paragraph [0063] may be produced, forexample, in accordance with the method disclosed in WO2017/0378830,using the compound (12-1) to (12-6) as the starting material, via thecompound (15c) wherein s=1.

<Method for Producing Compound (11d)>

The compound (11d) may be produced, for example, in accordance with themethod disclosed in JP-A-2016-037541 or WO2016/121211, using thecompound (13-1) to (13-6) as the starting material, via the compound(15d).

<Method for Producing Compound (11e)>

The compound (11e) may be produced, for example, in accordance with themethod disclosed in JP-A-2012-072272, using the compound (13-1) to(13-6) as the starting material, via the compound (15e) wherein v=0.

<Method for Producing Compound (11f)>

The compound (11f) wherein G(R⁶) is C(OH) may be produced, for example,in accordance with the method disclosed in JP-A-2016-037541, using thecompound (12-1) to (12-6) as the starting material, via the compound(15f).

<Method for Producing Compound (11g)>

The compound (11g) may be produced, for example, in accordance with themethod disclosed in WO2016/121211, by polymerizing CH₂═CHSi(OCH₃)₃,CH₂═CHCH₂Si(OCH₃)₃ or the like, using the compound (14-1) to (14-6) asan initiator.

[Fluorinated Ether Composition]

The fluorinated ether composition of the present invention (hereinaftersometimes referred to as “the present composition”) comprises at leastone type of the present compound and other fluorinated ether compound.

As other fluorinated ether compound, a fluorinated ether compound formedas a by-product during production of the present compound (hereinaftersometimes referred to as “by-product fluorinated ether compound”) and aknown fluorinated ether compound used in the same applications as thepresent compound may be mentioned.

Other fluorinated ether compound is preferably one unlikely to impairthe properties of the present compound.

As the by-product fluorinated ether compound, unreacted compounds (2) to(5); and fluorinated ether compounds formed through isomerization ofsome of the allyl groups into an inner olefin accompanyinghydrosilylation during the production of the compound (1) may, forexample, be mentioned.

As the known fluorinated ether compound, a commercially availablefluorinated ether compound may, for example, be mentioned. In a casewhere the present composition contains a known fluorinated ethercompound, it may have new effects such as compensation for theproperties of the present compound.

The content of the present compound is preferably at least 60 mass % andless than 100 mass %, more preferably at least 70 mass % and less than100 mass %, particularly preferably at least 80 mass % and less than 100mass % in the present composition.

The content of other fluorinated ether compound is preferably more than0 mass % and at most 40 mass %, more preferably more than 0 mass % andat most 30 mass %, particularly preferably more than 0 mass % and atmost 20 mass % in the present composition.

The total content of the present compound and other fluorinated ethercompound is preferably from 80 to 100 mass %, particularly preferablyfrom 85 to 100 mass % in the present composition.

When the content of the present compound and the content of otherfluorinated ether compound are within the above ranges, the surfacelayer is more excellent in initial water/oil repellency, abrasionresistance, fingerprint stain removability and light resistance.

The present composition may contain a component other than the presentcompound and other fluorinated ether compound within a range not toimpair the effects of the present invention.

Other component may, for example, be a by-product formed duringproduction of the present compound or the known fluorinated ethercompound (excluding the by-product fluorinated ether compound) or acompound inevitable in production such as an unreacted raw material.

Further, known additives such as an acid catalyst or a basic catalyst topromote hydrolysis and condensation reaction of the hydrolyzable silylgroup may be mentioned. The acid catalyst may, for example, behydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoricacid, sulfonic acid, methanesulfonic acid or p-toluenesulfonic acid. Thebasic catalyst may, for example, be sodium hydroxide, potassiumhydroxide or ammonia.

The content of other component is preferably from 0 to 9.999 mass %,particularly preferably from 0 to 0.99 mass % in the presentcomposition.

[Coating Liquid]

The coating liquid of the present invention (hereinafter sometimesreferred to as “the present coating liquid”) comprises the presentcompound or the present composition, and a liquid medium. The coatingliquid may be a solution or a dispersion.

The liquid medium is preferably an organic solvent. The organic solventmay be a fluorinated organic solvent, may be a non-fluorinated organicsolvent, or may contain both solvents.

The fluorinated organic solvent may, for example, be a fluorinatedalkane, a fluorinated aromatic compound, a fluoroalkyl ether, afluorinated alkylamine, a fluoroalcohol, etc.

The fluorinated alkane is preferably a C₄₋₈ compound. Commerciallyavailable products may, for example, be C₆F₁₃H (manufactured by AsahiGlass Company, Limited, ASAHIKLIN (registered trademark) AC-2000),C₆F₁₃C₂H₅ (manufactured by Asahi Glass Company, Limited, ASAHIKLIN(registered trademark) AC-6000), and C₂F₅CHFCHFCF₃ (manufactured byChemours, Vertrel (registered trademark) XF).

The fluorinated aromatic compound may, for example, behexafluorobenzene, trifluoromethylbenzene, perfluorotoluene orbis(trifluoromethyl)benzene.

The fluoroalkyl ether is preferably a C₁₋₄ compound. Commerciallyavailable products may, for example, be CF₃CH₂OCF₂CF₂H (manufactured byAsahi Glass Company, Limited, ASAHIKLIN (registered trademark) AE-3000),C₄F₉OCH₃ (manufactured by 3M, Novec (registered trademark) 7100),C₄F₉OC₂H₅ (manufactured by 3M, Novec (registered trademark) 7200), andC₂F₅CF(OCH₃)C₃F₇ (manufactured by 3M, Novec (registered trademark)7300),

The fluorinated alkylamine may, for example, be perfluorotripropylamineor perfluorotributylamine,

The fluoroalcohol may, for example, be 2,2,3,3-tetrafluoropropanol,2,2,2-trifluoroethanol or hexafluoroisopropanol.

The non-fluorinated organic solvent is preferably a compound consistingsolely of hydrogen atoms and carbon atoms, or a compound consisting ofonly hydrogen atoms, carbon atoms and oxygen atoms, and may, forexample, be a hydrocarbon-type solvent, an alcohol-type organic solvent,a ketone-type organic solvent, an ether-type organic solvent, or anester-type organic solvent.

The content of the present compound or the present composition ispreferably from 0.001 to 10 mass %, particularly preferably from 0.01 to1 mass % in the present coating liquid.

The content of the liquid medium is preferably from 90 to 99.999 mass %,particularly preferably from 99 to 99.99 mass % in the present coatingliquid.

[Article]

The article of the present invention (hereinafter sometimes referred toas “the present article” has a surface layer formed of the presentcompound or the present composition on the surface of a substrate.

The surface layer contains the present compound in a state where some orall of hydrolyzable silyl groups in the present compound are hydrolyzedand subjected to dehydration condensation reaction.

The thickness of the surface layer is preferably from 1 to 100 nm,particularly preferably from 1 to 50 nm. When the thickness of thesurface layer is at least the lower limit value of the above range, theeffect by the surface treatment is likely to be sufficiently obtained.When the thickness of the surface layer is at most the upper limit valueof the above range, utilization efficiency will be high. The thicknessof the surface layer can be calculated from the oscillation period ofthe interference pattern of the reflected X-ray, obtained by X-rayreflectance method using an X-ray diffractometer for thin film analysis(manufactured by Rigaku Corporation, ATX-G).

The substrate is not particularly limited so long as it is a substratewhich is desired to have water/oil repellency imparted. The material ofthe substrate may, for example, be a metal, a resin, glass, sapphire,ceramic, stone or a composite material thereof. The glass may bechemically tempered. The substrate may have a primer film such as a SiO₂film formed on its surface.

As the substrate, a substrate for a touch panel or a substrate fordisplay is preferred, and a substrate for a touch panel is particularlypreferred. As the material of a substrate for a touch panel, glass or atransparent resin is preferred.

[Method for Producing Article]

The present article may be produced, for example, by the followingmethod.

A method of treating the surface of a substrate by dry coating methodusing the present compound or the present composition, to form a surfacelayer on the surface of the substrate.

A method of applying the coating liquid to the surface of a substrate bywet coating method, and removing the liquid medium to form a surfacelayer on the surface of the substrate.

As the dry coating method, a method such as vacuum deposition, CVD orsputtering may be mentioned. With a view to suppressing thedecomposition of the present compound and from the viewpoint ofsimplicity of apparatus, vacuum deposition method is preferred. At thetime of vacuum deposition, a pelletized material having a metal porousproduct of iron, steel of the like impregnated with the present compoundor the present composition may be used.

The wet coating method may, for example, be a spin coating method, awipe coating method, a spray coating method, a squeegee coating method,a dip coating method, a die coating method, an ink-jet method, a flowcoating method, a roll coating method, a casting method, aLangmuir-Blodgett method, or a gravure coating method.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples, but the present invention is not limited to theseExamples. Hereinafter, “%” is “mass %” unless otherwise specified. Ex.1, 3, 5, 7, 9 and 11 are Examples of the present invention, and Ex. 2,4, 6, 8, 10 and 12 are Comparative Examples.

Ex. 1 Ex. 1-1

Into a 100 mL three-necked flask, 3.50 g of HOCH₂CF₂CF₂CF₂CH₂OH, 39.5 gof the compound (21-1) obtained by the method disclosed in Ex. 1 of U.S.Pat. No. 4,740,579 were put and stirred at 60° C. 0.64 g oftrifluoromethanesulfonic acid was dropwise added, followed by stirringfor 24 hours. The crude product was dissolved in 300 mL ofdichloromethane and washed twice with a mixed solution of 50 mL of a 35mass % hydrogen peroxide solution, 100 mL of a 10 mass % aqueous sodiumhydroxide solution and 250 mL of a saturated salt solution and furtherwashed twice with 300 mL of a saturated salt solution. The recoveredorganic phase was concentrated by an evaporator and purified by silicagel column chromatography (developing solvent: CF₃CH₂OCF₂CF₂H(manufactured by Asahi Glass Company, Limited, AE-3000)) to obtain 35.5g (yield: 82.6%) of compound (22-1).HOCH₂CF₂CF₂CF₂CH₂O(CH₂O—CH₂CF₂CF₂CF₂CH₂O)_(x3)H  (22-1)

NMR spectrum of compound (22-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: tetramethylsilane (TMS)δ(ppm): 4.8(22H), 4.0(48H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −121(44F),−123(4F), −126(24F).

Mean value of unit number x3: 11, number average molecular weight ofcompound (22-1): 2,680.

Ex. 1-2

Into a 100 mL eggplant flask, 35.0 g of the compound (22-1) obtained inEx. 1-1, 2.75 g of sodium fluoride powder and 30 g of AE-3000 were put,and 21.7 g of CF₃CF₂CF₂OCF(CF₃)C(O)F was added. Under a nitrogenatmosphere, the mixture was stirred at 50° C. for 24 hours. Afterremoving the sodium fluoride powder by a pressure filter, excessCF₃CF₂CF₂OCF(CF₃)COF and AE-3000 were distilled off under reducedpressure. The obtained crude product was diluted with C₆F₁₃H(manufactured by Asahi Glass Company, Limited, AC-2000) and passedthrough a silica gel column, whereupon the collected solution wasconcentrated by an evaporator to obtain 42.1 g (yield: 97.5%) ofcompound (23-1-1).CF₃CF₂CF₂OCF(CF₃)C(O)OCH₂CF₂CF₂CF₂CH₂O(CH₂O—CH₂CF₂CF₂CF₂CH₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (23-1-1)

NMR spectrum of compound (23-1-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 4.8(26H),4.0(44H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −79(2F),−81(6F), −82(6F), −86(2F), −120(48F), −126(24F), −129(4F), −132(2F).

Mean value of unit number x3: 11, number average molecular weight ofcompound (23-1-1): 3,300.

Ex. 1-3

At a gas outlet of a 500 mL nickel autoclave, a condenser maintained at20° C., a NaF pellet packed layer and a condenser maintained at 0° C.were installed in series. A liquid returning line to return the solutioncollected from the condenser maintained at 0° C. to the autoclave wasinstalled.

Into the autoclave, 250 g of ClCF₂CFCl₂ (hereinafter sometimes referredto as “R-113”) was put and stirred while maintaining the temperature at25° C. Into the autoclave, nitrogen gas was blown at 25° C. for onehour, and then, 20% fluorine gas was blown at 25° C. for one hour at aflow rate of 4.7 L/hour. While blowing the 20% fluorine gas at the sameflow rate, a solution having 20.0 g of the compound (23-1-1) obtained inEx. 1-2 dissolved in 100 g of R-113, was injected into the autoclaveover a period of 4 hours. While blowing the 20% fluorine gas at the sameflow rate, the internal pressure of the autoclave was raised to 0.15 MPa(gauge pressure). Into the autoclave, 4 mL of a benzene solutioncontaining 0.03 g/mL of benzene in R-113, was injected while heating to40° C. from 25° C., and then the benzene solution inlet of the autoclavewas closed. After stirring for 15 minutes, 4 mL of the benzene solutionwas again injected while maintaining the temperature at 40° C., and thenthe inlet was closed. The same operation was repeated four more times.The total amount of benzene injected was 0.6 g. While blowing the 20%fluorine gas at the same flow rate, stirring was continued for 1 hour.The pressure in the autoclave was brought to atmospheric pressure, andnitrogen gas was blown in for 1 hour. The content of the autoclave wasconcentrated by an evaporator to obtain 27.5 g (yield: 99.5%) ofcompound (24-1-1).CF₃CF₂CF₂OCF(CF₃)C(O)OCF₂CF₂CF₂CF₂CF₂O(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (24-1-1)

NMR spectrum of compound (24-1-1):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−80(2F), −81(6F), −82(6F), −84(4F), −85(44F), −87(2F), −118(4F),−122(20F), −123(4F), −125(44F), −130(4F), −133(2F).

Mean value of unit number x3: 11, number average molecular weight ofcompound (24-1-1): 4,560.

Ex. 1-4

Into a round bottom flask made of a tetrafluoroethylene/perfluoro(alkoxyvinyl ether) copolymer (hereinafter sometimes referred to as “PFA”),27.0 g of the compound (24-1-1) obtained in Ex. 1-3 and 30 g of AE-3000were put. The mixture was stirred while cooling in an ice bath, and in anitrogen atmosphere, 1.9 g of methanol was slowly dropwise added from adropping funnel. While bubbling with nitrogen, the mixture was stirredfor 12 hours. The reaction mixture was concentrated by an evaporator toobtain 22.9 g (yield: 98.7%) of compound (12-1-1).CH₃OC(O)CF₂CF₂CF₂CF₂O(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂C(O)OCH₃  (12-1-1)

NMR spectrum of compound (12-1-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9 (6H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−85(44F), −118(4F), −122(20F), −123(4F), −126(44F).

Mean value of unit number x3-1: 10, number average molecular weight ofcompound (12-1-1): 3,920.

Ex. 1-5

Into a 50 mL eggplant flask, 10.0 g of the compound (12-1-1) obtained inEx. 1-4, 0.90 g of H₂NCH₂C(CH₂CH═CH₂)₃ and 10 g of AE-3000 were put andstirred for 12 hours. The obtained reaction mixture was diluted with30.0 g of AE-3000 and purified by silica gel column chromatography(developing solvent: AE-3000) to obtain 10.2 g (yield: 95.5%) ofcompound (15c-1).

NMR Spectrum of compound (15c-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(12H),3.4(4H), 5.2(12H), 6.2 to 5.9(6H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−85(44F), −120(4F), −122(20F), −123(4F), −126(44F).

Mean value of unit number x3-1: 10, number average molecular weight ofcompound (15c-1): 4,190.

Ex. 1-6

Into a 10 mL PFA sample tube, 5.0 g of the compound (15c-1) obtained inEx. 1-5, 0.03 g of a xylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, 1.43 g ofHSi(OCH₃)₃, 0.01 g of aniline and 5.0 g of1,3-bis(trifluoromethyl)benzene were put and stirred at 40° C. for 10hours. After completion of the reaction, the solvent, etc. weredistilled off under reduced pressure, followed by filtration through amembrane filter having a pore size of 1.0 μm to obtain 5.82 g (yield:99.1%) of compound (11c-1).

NMR Spectrum of compound (11c-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(12H),1.3 to 1.6(24H), 3.4(4H), 3.7(54H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−85(44F), −120(4F), −122(20F), −123(4F), −126(44F).

Mean value of unit number x3-1: 10, number average molecular weight ofcompound (11c-1): 4,920. The proportion of the unit (α) is 0.45, fromm1=11, m4=1 and m5=10.

Ex. 2 Ex. 2-1

Into a 50 mL eggplant flask, 20.0 g of a perfluoropolyether compoundhaving a carboxy group on both terminals and having (CF₂O) and (CF₂CF₂O)randomly bonded as the unit of the poly(oxyperfluoroalkylene chain)(manufactured by Solvay Solexis, FOMBLIN (registered trademark)ZDIAC4000), 5.0 g of methanol and 20 g of AE-3000 were put and stirredat 50° C. for 12 hours. The solvent, etc. were distilled off from theobtained reaction mixture, followed by dilution with 50.0 g of AE-3000and purification by silica gel column chromatography (developingsolvent: AE-3000) to obtain 14.3 g (yield: 71.0%) of compound (42-1).CH₃OC(O)CF₂O{(CF₂O)_(x1)(CF₂CF₂O)_(x2)}CF₂C(O)OCH₃  (42-1)

NMR Spectrum of compound (42-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(6H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(38F), −78(2F), −80(2F), −89 to −91(84F).

Mean value of unit number x1: 20, mean value of unit number x2: 21,number average molecular weight of compound (42-1): 3,990.

Ex. 2-2

In the same manner as in Ex. 1-5 except that 10.0 g of the compound(42-1) was used instead of the compound (12-1-1), 10.3 g (yield: 96.6%)of compound (45c-1) was obtained.

NMR Spectrum of compound (45c-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(12H),3.4(4H), 5.2(12H), 6.2 to 5.9(6H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(38F), −77(2F), −79(2F), −89 to −91(84F).

Mean value of unit number x1: 20, mean value of unit number x2: 21,number average molecular weight of compound (45c-1): 4,260.

Ex. 2-3

In the same manner as in Ex. 1-6 except that 5.0 g of the compound(45c-1) was used instead of the compound (15c-1), 5.78 g (yield: 98.6%)of compound (41c-1) was obtained.

NMR Spectrum of compound (41c-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(12H),1.3 to 1.6(24H), 3.4(4H), 3.7(54H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(38F), −77(2F), −79(2F), −89 to −91(84F).

Mean value of unit number x1: 20, mean value of unit number x2: 21,number average molecular weight of compound (41c-1): 4,990. Theproportion of the unit (α) is 0 from m5=m6=0.

Ex. 3 Ex. 3-1

In the same manner as in Ex. 1-1 except that 1.5 g of CF₃CH₂OH was usedinstead of HOCH₂CF₂CF₂CF₂CH₂OH, the amount of the compound (21-1) waschanged to 35.0 g, and the amount of trifluoromethanesulfonic acid waschanged to 0.70 g, 24.4 g (yield: 66.8%) of compound (22-3-1) wasobtained.CF₃CH₂O(CH₂O—CH₂CF₂CF₂CF₂CH₂O)_(x3)H  (22-3-1)

NMR Spectrum of compound (22-3-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 4.8(22H),4.0(44H), 3.9(2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −75(3F),−121(42F), −123(2F), −126(22F).

Mean value of unit number x3: 11, number average molecular weight ofcompound (22-3-1): 2,570.

Ex. 3-2

In the same manner as in Ex. 1-2 except that 24.0 g of the compound(22-3-1) was used instead of the compound (22-1), the amount of sodiumfluoride was changed to 1.96 g, and the amount of CF₃CF₂CF₂OCF(CF₃)C(O)Fwas changed to 9.32 g, 26.3 g (yield: 97.7%) of compound (23-3-1) wasobtained.CF₃CH₂O(CH₂O—CH₂CF₂CF₂CF₂CH₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (23-3-1)

NMR Spectrum of compound (23-3-1):

1H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 4.8(24H),4.0(42H), 3.9(2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −75(3F),−79(1F), −81(3F), −82(3F), −86(1F), −120(44F), −126(22F), −129(2F),−132(1F).

Mean value of unit number x3: 11, number average molecular weight ofcompound (23-3-1): 2,880.

Ex. 3-3

In the same manner as in Ex. 1-3 except that 20.0 g of the compound(23-3-1) was used instead of the compound (23-1-1), 28.2 g (yield:98.9%) of compound (24-3-1) was obtained.CF₃CF₂O(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (24-3-1)

NMR Spectrum of compound (24-3-1):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−80(1F), −81(3F), −82(3F), −84(2F), −85(42F), −87(4F), −90(2F),−118(2F), −122(20F), −123(2F), −125(42F), −130(2F), −133(1F).

Mean value of unit number x3: 11, number average molecular weight ofcompound (24-3-1): 4,100.

Ex. 3-4

In the same manner as in Ex. 1-4 except that 27.0 g of the compound(24-3-1) was used instead of the compound (24-1-1) and the amount ofmethanol was changed to 1.05 g, 24.4 g (yield: 98.0%) of compound(12-3-1) was obtained.CF₃CF₂O(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂C(O)OCH₃  (12-3-1)

NMR Spectrum of compound (12-3-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−85(42F), −87(3F), −90(2F), −118(2F), −122(20F), −123(2F), −126(42F).

Mean value of unit number x3-1: 10, number average molecular weight ofcompound (12-3-1): 3,780.

Ex. 3-5

In the same manner as in Ex. 1-5 except that 10.0 g of the compound(12-3-1) was used instead of the compound (12-1-1) and the amount ofH₂NCH₂C(CH₂CH═CH₂)₃ was changed to 0.50, 9.9 g (yield: 95.6%) ofcompound (15c-2) was obtained.CF₃CF₂O(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂C(O)NHCH₂C(CH₂CH═CH₂)₃  (15c-2)

NMR Spectrum of compound (15c-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(6H),3.4(2H), 5.2(6H), 6.2 to 5.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−85(42F), −87(3F), −90(2F), −120(2F), −122(20F), −123(2F), −126(42F).

Mean value of unit number x3-1: 10, number average molecular weight ofcompound (15c-2): 3,910.

Ex. 3-6

In the same manner as in Ex. 1-6 except that 5.0 g of the compound(15c-2) was used instead of the compound (15c-1), the amount of thexylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was changedto 0.02 g, the amount of HSi(OCH₃)₃ was changed to 0.78 g, and theamount of aniline was changed to 0.005 g, 5.45 g (yield: 99.7%) ofcompound (11c-2) was obtained.CF₃CF₂O(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂OCF₂CF₂CF₂CF₂C(O)NHCH₂C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (11c-2)

NMR Spectrum of compound (11c-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(6H), 1.3to 1.6(12H), 3.4(2H), 3.7(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −51(22F),−85(42F), −87(3F), −90(2F), −120(2F), −122(20F), −123(2F), −126(42F).

Mean value of unit number x3-1: 10, number average molecular weight ofcompound (11c-2): 4,280. The proportion of the unit (α) is 0.48 fromm1=11 and m5=10.

Ex. 4

Compound (41c-2) was obtained in accordance with the method disclosed inWO2017/38830, Ex. 16.CF₃CF₂CF₂O(CF₂CF₂O)(CF₂CF₂O){(CF₂O/)_(x1)(CF₂CF₂O)_(x2)}CF₂C(O)NHCH₂C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (41c-2)

NMR Spectrum of compound (41c-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(6H), 1.3to 1.6(12H), 3.4(2H), 3.7(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(38F), −78(2F), −80(2F), −89 to −91(84F).

Mean value of unit number x1: 22, mean value of unit number x2: 19,number average molecular weight of compound (41c-2): 4,480. Theproportion of the unit (α) is 0 from m5=m6=0.

Ex. 5 Ex. 5-1

Compound (31-2) was obtained in accordance with the method disclosed inJournal of Fluorine Chemistry, vol. 126, 2005, p. 521 to 527 except thatHO(CH₂)₆OH was used instead of HO(CH₂)₄OH.CF₂═CFO(CF₂)₅C(O)OCH₃  (31-2)

NMR Spectrum of compound (31-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −85(2F),−114(1F), −118(2F), −122(3F), −123(2F), −126(2F), −135(1F).

Ex. 5-2

The compound (31-2) was reduced by the method disclosed in PatentDocument 1, Ex. 1-1, to obtain compound (32-2).CF₂═CFO(CF₂)₅CH₂OH  (32-2)

NMR Spectrum of compound (32-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 4.0(2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −85(2F),−114(1F), −121(2F), −122(3F), −123(2F), −126(2F), −135(1F).

Ex. 5-3

The compound (32-2) was subjected to addition polymerization inaccordance with the method disclosed in Patent Document 1, Ex. 6,followed by column purification to obtain compound (22-6-1).CH₃O(CF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O)_(x3)H  (22-6-1)

NMR Spectrum of compound (22-6-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.0(2H), 4.4(18H), 6.1(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −86(20F),−91(20F), −121(38F), −122(20F), −123(2F), −126(20F), −145(10F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (22-6-1): 3,810.

Ex. 5-4

In the same manner as in Ex. 1-2 except that 30.0 g of the compound(22-6-1) was used instead of the compound (22-1), the amount of thesodium fluoride powder was changed to 1.96 g, and the amount ofCF₃CF₂CF₂OCF(CF₃)C(O)F was changed to 9.32 g, 32.1 g (yield: 98.9%) ofcompound (23-6-1) was obtained.CH₃O(CF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (23-6-1)

NMR Spectrum of compound (23-6-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.4(18H), 4.8(2H), 6.1(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −79(1F),−81(3F), −82(3F), −86(21F), −91(20F), −120(2F), −121(38F), −122(20F),−126(20F), −129(2F), −131(1F), −145(10F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (23-6-1): 4,120.

Ex. 5-5

In the same manner as in Ex. 1-3 except that 20.0 g of the compound(23-6-1) was used instead of the compound (23-1-1), 22.4 g (yield:97.9%) of compound (24-6-1) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (24-6-1)

NMR Spectrum of compound (24-6-1):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−80(1F), −82(6F), −83(2F), −85(38F), −87(1F), −91(40F), −122(40F),−125(40F), −130(2F), −132(1F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (24-6-1): 4,720.

Ex. 5-6

In the same manner as in Ex. 1-4 except that 22.0 g of the compound(24-6-1) was used instead of the compound (24-1-1) and the amount ofmethanol was changed to 0.75 g, 20.2 g (yield: 98.5%) of compound(12-6-1) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CF₂C(O)OCH₃  (12-6-1)

NMR Spectrum of compound (12-6-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−85(38F), −91(40F), −118(2F), −122(38F), −123(2F), −125(38F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (12-6-1): 4,400.

Ex. 5-7

In the same manner as in Ex. 1-5 except that 10.0 g of the compound(12-6-1) was used instead of the compound (12-1-1) and the amount ofH₂NCH₂C(CH₂CH═CH₂)₃ was changed to 0.45 g, 9.6 g (yield: 96.1%) ofcompound (15c-3) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CF₂C(O)NHCH₂C(CH₂CH═CH₂)₃  (15c-3)

NMR Spectrum of compound (15c-3):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(6H),3.4(2H), 5.2(6H), 6.2 to 5.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−85(38F), −91(40F), −120(2F), −122(38F), −125(40F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (15c-3): 4,530.

Ex. 5-8

In the same manner as in Ex. 1-6 except that 5.0 g of the compound(15c-3) was used instead of the compound (15c-1), the amount of thexylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3,-tetramethyldisiloxane complex was changedto 0.02 g, the amount of HSi(OCH₃)₃ was changed to 0.67 g, and theamount of aniline was changed to 0.005 g, 5.32 g (yield: 98.4%) ofcompound (11c-3) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CF₂CF₂C(O)NHCH₂C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (11c-3)

NMR Spectrum of compound (11c-3):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(6H), 1.3to 1.6(12H), 3.4(2H), 3.7(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−85(38F), −91(40F), −120(2F), −122(38F), −125(40F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (11c-3): 4,900. The proportion of the unit (α) is 0.48 fromm2=11 and m6=10.

Ex. 6 Ex. 6-1

Compound (41c-3) was obtained in accordance with the method disclosed inWO2017/38830, Ex 11.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂C(O)NHCH₂C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (41c-3)

Mean value of unit number x3: 14, number average molecular weight ofcompound (41c-3): 5,270. The proportion of the unit (α) is 0 fromm5=m6=0.

Ex. 7 to 12 Production and Evaluation of Article

Using the compound obtained in each of Ex. 1 to 6, surface treatment ofa substrate was conducted to obtain an article in each of Ex. 7 to 12.As the surface treatment method, in each Ex., the following dry coatingand wet coating method were, respectively, employed. As the substrate,chemically tempered glass was used. With respect to the obtainedarticle, evaluations were carried out by the following methods. Theresults are shown in Table 1.

(Dry Coating Method)

The dry coating was carried out by using a vacuum deposition apparatus(manufactured by ULVAC Co., VTR-350M) (vacuum deposition method). 0.5 gof the compound obtained in each of Ex. 1 to 6 and 13 to 16 was filledin a boat made of molybdenum in the vacuum deposition apparatus, andinside of the vacuum deposition apparatus was evacuated to a level of atmost 1×10⁻³ Pa. The boat having the compound placed therein, was heatedat a temperature raising rate of at most 10° C./min, and at the timewhen the vapor deposition rate by a quartz oscillator film thicknessmeter exceeded 1 nm/sec, the shutter was opened to initiate filmdeposition on the surface of a substrate. When the film thickness becameabout 50 nm, the shutter was closed to terminate film deposition on thesurface of the substrate. The substrate on which the compound wasdeposited, was subjected to heat treatment at 200° C. for 30 minutes,followed by washing with dichloropentafluoropropane (manufactured byAsahi Glass Company, Limited, AK-225), to obtain an article having asurface layer on the surface of the substrate.

(Wet Coating Method)

The compound obtained in each of Ex. 1 to 6 and 13 to 16, and C₄F₉OC₂H₅(manufactured by 3M, Novec (registered trademark) 7200) as a medium,were mixed to prepare a coating liquid having a solid contentconcentration of 0.05%. A substrate was dipped in the coating liquid andallowed to stand for 30 minutes, whereupon the substrate was taken out(dip coating method). The coating film was dried at 200° C. for 30minutes and washed with AK-225, to obtain an article having a surfacelayer on the surface of the substrate.

(Evaluation Methods)

<Method for Measuring Contact Angle>

The contact angle of about 2 μL of distilled water or n-hexadecaneplaced on the surface of the surface layer, was measured by using acontact angle measuring apparatus (manufactured by Kyowa InterfaceScience Co., Ltd., DM-500). Measurements were conducted at fivedifferent points on the surface of the surface layer, and the averagevalue was calculated. For the calculation of the contact angle, a 2θmethod was employed.

<Initial Contact Angle>

With respect to the surface layer, the initial water contact angle andthe initial n-hexadecane contact angle were measured by theabove-described measuring method. The evaluation standards are asfollows.

Initial water contact angle:

⊚ (excellent): at least 115 degrees.

◯ (good): at least 110 degrees and less than 115 degrees.

Δ (acceptable): at least 100 degrees and less than 110 degrees.

× (poor): less than 100 degrees.

Initial n-hexadecane contact angle:

⊚ (excellent): at least 66 degrees.

◯ (good): at least 65 degrees and less than 66 degrees.

Δ (acceptable): at least 63 degrees and less than 65 degrees.

× (poor): less than 63 degrees.

<Abrasion Resistance (Steel Wool)>

With respect to the surface layer, in accordance with JIS L0849: 2013(ISO 105-X12: 2001), using a reciprocating traverse testing machine(manufactured by KNT Co.), steel wool Bon Star (#0000) was reciprocated10,000 times under a pressure of 98.07 kPa at a speed of 320 cm/min,whereupon the water contact angle was measured. The smaller the decreasein water repellency (water contact angle) after the abrasion, thesmaller the decrease in performance due to friction, and the better theabrasion resistance. The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after reciprocation of10,000 times is at most 2 degrees.

◯ (good): The change in water contact angle after reciprocation of10,000 times is more than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after reciprocation of10,000 times is more than 5 degrees and at most 10 degrees.

× (poor): The change in water contact angle after reciprocation of10,000 times is more than 10 degrees.

<Abrasion Resistance (Eraser)>

With respect to the surface layer, in accordance with JIS L0849: 2013(ISO 105-X12: 2001), using a reciprocating traverse testing machine(manufactured by KNT Co.), Rubber Eraser (manufactured by Minoan) wasreciprocated 30,000 times under a load of 4.9 N at a speed of 60 rpm,whereupon the water contact angle was measured. The smaller the decreasein water repellency (water contact angle) after the abrasion, thesmaller the decrease in performance due to friction, and the better theabrasion resistance. The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after reciprocation of30,000 times is at most 2 degrees.

◯ (good): The change in water contact angle after reciprocation of30,000 times is more than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after reciprocation of30,000 times is more than 5 degrees and at most 10 degrees.

× (poor): The change in water contact angle after reciprocation of30,000 times is more than 10 degrees.

<Fingerprint Stain Removability>

An artificial fingerprint liquid (liquid consisting of oleic acid andsqualene) was deposited on a flat surface of a silicon rubber plug, andthen, extra oil was wiped off by a nonwoven fabric (manufactured byAsahi Kasei Corporation, BEMCOT (registered trademark) M-3), to preparea stamp for fingerprint. The fingerprint stamp was placed on the surfacelayer and pressed under a load of 9.8 N for 10 seconds. The haze at aportion having a fingerprint adhered, was measured by a haze meter andtaken as an initial value. With respect to the portion having afingerprint adhered, using a reciprocating traverse testing machine(manufactured by KNT Co.) having tissue paper attached, wiping wascarried out under a load of 4.9 N. The value of haze was measured everyone reciprocation for wiping, and the number of wiping times until thehaze became at most 10% from the initial value, was measured. Thesmaller the number of wiping times, the easier the removal offingerprint stain, and the better the fingerprint stain removability.The evaluation standards are as follows.

⊚ (excellent): The number of wiping times is at most 3 times.

◯ (good): The number of wiping times is from 4 to 5 times.

Δ (acceptable): The number of wiping times is from 6 to 8 times.

× (poor): The number of wiping times is at least 9 times.

<Light Resistance>

To the surface layer, by means of a tabletop xenon arc lamp typeaccelerated light resistance testing machine (manufactured by Toyo SeikiSeisaku-sho, Ltd., SUNTEST XLS+), light (650 W/m², 300 to 700 nm) wasapplied at a black panel temperature of 63° C. for 1,000 hours,whereupon the water contact angle was measured. The smaller the decreasein water contact angle after the accelerated light resistance test, thesmaller the decrease in performance due to light, and the better thelight resistance. The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after the acceleratedlight resistance test is at most 2 degrees.

◯ (good): The change in water contact angle after the accelerated lightresistance test is more than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after the acceleratedlight resistance test is more than 5 degrees and at most 10 degrees.

× (poor): The change in water contact angle after the accelerated lightresistance test is more than 10 degrees.

<Lubricity>

The dynamic friction coefficient of the surface layer to an artificialskin (manufactured by Idemitsu Technofine Co., Ltd., PBZ13001) wasmeasured by means of a load variation type friction abrasion test system(manufactured by Shinto Scientific Co., Ltd., HHS2000) under conditionsof a contact area of 3 cm×3 cm and a load of 0.98N. The smaller thedynamic friction coefficient, the better the lubricity. The evaluationstandards are as follows.

⊚ (excellent): The dynamic friction coefficient is at most 0.2.

◯ (good): The dynamic friction coefficient is more than 0.2 and at most0.3.

Δ (acceptable): The dynamic friction coefficient is more than 0.3 and atmost 0.4.

× (poor): The dynamic friction coefficient is more than 0.4.

TABLE 1 Ex. 7 8 (Comparison) 9 10 (Comparison) 11 12 (Comparison)Fluorinated ether compound Compound Compound Compound Compound CompoundCompound (11c-1) (41c-1) (11c-2) (41c-2) (11c-3) (41c-3) Dry Initialcontact Water ◯ Δ ⊚ ⊚ ⊚ ⊚ coating angle n-Hexadecane Δ X ⊚ ⊚ ⊚ ⊚ methodAbrasion resistance (steel wool) Δ X ◯ Δ ◯ Δ Abrasion resistance(eraser) Δ Δ Δ Δ Δ Δ Fingerprint stain removability ◯ ◯ ⊚ ⊚ ⊚ ⊚ Lightresistance Δ X Δ X ◯ X Lubricity Δ ◯ ◯ ⊚ Δ Δ Wet Initial contact Water ◯Δ ⊚ ⊚ ⊚ ⊚ coating angle n-Hexadecane Δ X ⊚ ⊚ ⊚ ⊚ method Abrasionresistance (steel wool) Δ X ◯ Δ Δ Δ Abrasion resistance (eraser) Δ X Δ XΔ X Fingerprint stain removability ◯ ◯ ⊚ ⊚ ⊚ ⊚ Light resistance Δ X Δ X◯ X Lubricity Δ ◯ ◯ ⊚ Δ Δ

It was confirmed that in Ex. 7, 9 and 11 in which the present inventionwas used, excellent initial water/oil repellency, abrasion resistanceand light resistance were achieved.

In Ex. 8 in which the compound (41c-1) having a hydrolyzable silyl groupon both terminals of the poly(oxyperfluoroalkylene) chain comprising(CF₂O) and (CF₂CF₂O) via a linking group was used, the initial oilrepellency, abrasion resistance and light resistance were inferior.

In Ex. 10 in which the compound (41c-2) having a hydrolyzable silylgroup on one terminal of the poly(oxyperfluoroalkylene) chain comprising(CF₂O) and (CF₂CF₂O) via a linking group was used, the abrasionresistance and light resistance were inferior.

In Ex. 12 in which the compound (41c-3) having a hydrolyzable silylgroup on one terminal of the poly(oxyperfluoroalkylene) chain comprising(CF₂CF₂O) and (CF₂CF₂CF₂CF₂O) via a linking group was used, the abrasionresistance and light resistance were inferior.

Ex. 13 Ex. 13-1

In a 500 mL three-necked flask, 40 g of HOCH₂CH₂CH₂CH₂CH₂CH₂OH, 59 g ofa 48% KOH aqueous solution, 68 g of tert-butyl alcohol and 61 g ofdeionized water were put, and 23 g of CF₃CF₂CF₂—O—CF═CF₂ was added,followed by stirring in a nitrogen atmosphere. The mixture was washedonce with a diluted aqueous hydrochloric acid solution, and the organicphase was recovered and concentrated under reduced pressure to obtain 27g of crude product (51-1).CF₃CF₂CF₂—O—CHF—CF₂OCH₂CH₂CH₂CH₂CH₂CH₂OH  (51-1)

NMR Spectrum of compound (51-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 1.3(4H),1.7(4H), 2.5(1H), 3.5(2H), 3.9(2H), 5.8(1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −82(3F),−84 to 87(2F), −89(2F), −130(2F), −146(1F).

Ex. 13-2

Into a 500 mL three-necked flask, 29 g of the compound (51-1) obtainedin Ex. 13-1, 294 g of AE-3000 and 12 g of triethylamine were put, and 19g of p-toluenesulfonyl chloride was added, followed by stirring in anitrogen atmosphere. The mixture was washed once with a diluted aqueoushydrochloric acid solution, and the organic phase was recovered,concentrated by an evaporator and purified by silica gel columnchromatography to obtain 18 g of product (51-2). (OTs: —O—SO₂-Ph-CH₃)CF₃CF₂CF₂—O—CHF—CF₂OCH₂CH₂CH₂CH₂CH₂CH₂OTs  (51-2)

NMR Spectrum of compound (51-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 1.3(4H),1.7(4H), 2.5(3H), 3.9(2H), 4.0(2H), 5.8(1H), 7.1 to 7.8(4H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −82(3F),−84 to 87(2F), −89(2F), −130(2F), −146(1F).

Ex. 13-3

Into a 300 mL three-necked flask, 4 g of the compound (51-2) obtained inEx. 13-2, 31 g of compound (60-1) (manufactured by Solvay Solexis,FLUOROLINK (registered trademark) D4000) and 160 g of1,3-bis(trifluoromethyl)benzene were put, and 12 g of cesium carbonatewas added, followed by stirring in a nitrogen atmosphere at 70° C. Thesolid was removed by filtration, the filtrate was washed with water, andthe organic phase was recovered, concentrated under reduced pressure andpurified by silica gel column chromatography to obtain 9 g of product(51-3).HO—CH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂—OH  (60-1)CF₃CF₂CF₂—O—CHF—CF₂OCH₂CH₂CH₂CH₂CH₂CH₂O—CH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂—OH  (51-3)

NMR Spectrum of compound (51-3):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 1.3(4H),1.7(4H), 2.5(1H), 3.5(2H), 3.8(2H), 4.0(2H), 4.2(2H), 5.8(1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(42F), −79(1F), −80(1F), −81(1F), −82(3F), −84(1F), −85 to −88(2F),−89 to −91(82F), −130(2F), −146(1F).

Mean value of unit number x1: 21, mean value of unit number x2: 20,number average molecular weight of compound (51-3): 4,050.

Ex. 13-4

Into a 100 mL eggplant flask, 12 g of the compound (51-3) and 2.3 g of asodium fluoride powder were put, and 9.3 g of CF₃CF₂CF₂OCF(CF₃)C(O)F wasadded, followed by stirring in a nitrogen atmosphere. The sodiumfluoride powder was removed by filtration and excessCF₃CF₂CF₂OCF(CF₃)C(O)F was distilled off under reduced pressure toobtain 12 g of compound (51-4).CF₃CF₂CF₂—O—CHF—CF₂OCH₂CH₂CH₂CH₂CH₂CH₂O—CH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂—OC(O)CF(CF₃)OCF₂CF₂CF₃  (51-4)

NMR Spectrum of compound (51-4):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 1.3(4H),1.7(4H), 2.5(1H), 3.5(2H), 4.0(2H), 4.2(2H), 4.7(2H), 5.8(1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(42F), −79 to −88(16F), −89 to −91(82F), −130(4F), −133(2F),−146(1F).

Mean value of unit number x1: 21, mean value of unit number x2: 20,number average molecular weight of compound (51-4): 4,450.

Ex. 13-5

At a gas outlet of a 1 L nickel autoclave, a condenser maintained at 20°C., a NaF pellet packed layer and a condenser maintained at 0° C. wereinstalled in series. A liquid returning line to return the solutioncollected from the condenser maintained at 0° C. to the autoclave wasinstalled.

Into the autoclave, 750 g of ClCF₂CFClCF₂OCF₂CF₂Cl (hereinaftersometimes referred to as CFE-419) was put and stirred while maintainingthe temperature at 25° C. Into the autoclave, nitrogen gas was blown at25° C. for one hour, and then, 20% fluorine gas was blown at 25° C. forone hour at a flow rate of 2.0 L/hour. While blowing the 20% fluorinegas at the same flow rate, a solution having 6.0 g of the compound(51-4) dissolved in 54 g of CFE-419, was injected into the autoclaveover a period of 1 hour. While blowing the 20% fluorine gas at the sameflow rate, the internal pressure of the autoclave was raised to 0.15 MPa(gauge pressure). Into the autoclave, 4 mL of a benzene solutioncontaining 0.05 g/mL of benzene in CFE-419, was injected while heatingto 40° C. from 25° C., and then the benzene solution inlet of theautoclave was closed. After stirring for 15 minutes, 4 mL of the benzenesolution was again injected while maintaining the temperature at 40° C.,and then the inlet was closed. The same operation was repeated threemore times. The total amount of benzene injected was 0.17 g. Whileblowing the 20% fluorine gas at the same flow rate, stirring wascontinued for 1 hour. The pressure in the autoclave was brought toatmospheric pressure, and nitrogen gas was blown in for 1 hour. Thecontent of the autoclave was concentrated by an evaporator to obtain 5.7g of compound (51-5).CF₃CF₂CF₂—O—CF₂—CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O—CF₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CF₂—OC(O)CF(CF₃)OCF₂CF₂CF₃  (51-5)

NMR Spectrum of compound (51-5):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(42F), −79 to −88(20F), −89 to −91(90F), −121(4F), −124(4F),−130(4F), −133(1F).

Mean value of unit number x1: 21, mean value of unit number x2: 20,number average molecular weight of compound (51-5): 4,550.

Ex. 13-6

Into a round bottomed flask made of PFA, 5.7 g of the compound (51-5)and 10 g of AK-225 were put. The mixture was stirred while cooling in anice bath, and in a nitrogen atmosphere, 10 g of methanol was slowlydropwise added from a dropping funnel, followed by stirring for 12hours. The reaction mixture was concentrated by an evaporator to obtain5.3 g of compound (51-6).CF₃CF₂CF₂—O—CF₂—CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O—CF₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)OCH₃  (51-6)

NMR Spectrum of compound (51-6):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(42F), −79 to −88(10F), −89 to −91(90F), −121(4F), −124(4F),−130(2F).

Mean value of unit number x1: 21, mean value of unit number x2: 20,number average molecular weight of compound (51-6): 4,200.

Ex. 13-7

Into a 50 mL eggplant flask, 4.7 g of the compound (51-6) obtained inEx. 13-6, 0.3 g of H₂NCH₂C(CH₂CH═CH₂)₃ and 10 g of AC-6000 were put andstirred for 12 hours. The obtained reaction mixture was purified bysilica gel column chromatography to obtain 3.1 g of compound (51-7).CF₃CF₂CF₂—O—CF₂—CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O—CF₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—CH₂C(CH₂CH═CH₂)₃  (51-7)

NMR Spectrum of compound (51-7):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(6H),3.4(2H), 5.2(6H), 5.9 to 6.2(3H)

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(42F), −79 to −88(10F), −89 to −91(90F), −121(4F), −124(4F),−130(2F).

Mean value of unit number x1: 21, mean value of unit number x2: 20,number average molecular weight of compound (51-7): 3,700.

Ex. 13-8

Into a 10 mL PFA sample tube, 1.5 g of the compound (51-7) obtained inEx. 13-7, 0.02 g of a xylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, 0.52 ofHSi(OCH₃)₃, 0.01 g of aniline and 2.3 g of AC-6000 were put and stirredat 40° C. After completion of the reaction, the solvent, etc. weredistilled off under reduced pressure, followed by filtration through amembrane filter having a pore size of 1.0 μm, to obtain 1.5 g ofcompound (51-8).CF₃CF₂CF₂—O—CF₂—CF₂OCF₂CF₂CF₂CF₂CF₂CF₂O—CF₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—CH₂C(CH₂CH₂CH₂Si(OCH₃)₃)₃  (51-8)

NMR Spectrum of compound (51-8):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(6H), 1.3to 1.6(12H), 3.4(2H), 3.7(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −52 to−56(42F), −79 to −88(10F), −89 to −91(90F), −121(4F), −124(4F),−130(2F).

Mean value of unit number x1: 21, mean value of unit number x2: 20,number average molecular weight of compound (51-8): 3,700. Theproportion of the unit (α) is 0.02 from m1=21, m2=22 and m6=1.

Ex. 14 Ex. 14-1

Into a 50 mL three-necked flask, 25 g of methanol and 0.5 g of potassiumcarbonate were put, and 8 g of the compound (32-2) was added, followedby stirring at room temperature for 12 hours. The mixture wasconcentrated and washed with a diluted aqueous hydrochloric acidsolution, and the organic phase was recovered and concentrated to obtain8 g of product (52-1).CH₃OCF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂OH  (52-1)

NMR Spectrum of compound (52-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.1(2H), 6.0(1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −85(2F),−93(2F), −123(4F), −124(2F), −126(2F), −145(1F).

Ex. 14-2

In accordance with the method disclosed in Patent Document 1 except thatthe compound (52-1) was used as methanol-added product, additionpolymerization was conducted, followed by column purification to obtaincompound (52-2).CH₃OCF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O(CF₂CHFO—CF₂CF₂CF₂CH₂O)_(x3)H  (52-2)

NMR Spectrum of compound (52-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.0(2H), 4.4(20H), 6.1(11H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −86(20F),−91(20F), −120(2F) −121(20F), −122(2F), −123(4F), −126(2F),−128(22F)-145(11F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (52-2): 3,190.

Ex. 14-3

In the same manner as in Ex. 1-2 except that 22 g of the compound (52-2)was used instead of the compound (22-1), the amount of the sodiumfluoride powder was changed to 4.3 g, and the amount ofCF₃CF₂CF₂OCF(CF₃)C(O)F was changed to 11.5 g, 24 g (yield: 97.3%) ofcompound (52-3) was obtained.CH₃OCF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O(CF₂CHFO—CF₂CF₂CF₂CH₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (52-3)

NMR Spectrum of compound (52-3):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.4(20H), 4.8(2H), 6.1(11H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −79(1F),−81(3F), −82(3F), −86(21F), −91(20F), −120(2F) −121(22F), −122(2F),−123(2F), −126(2F), −128(22F), −131(2F), −133(1F), −145(11F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (52-3): 3500.

Ex. 14-4

In the same manner as in Ex. 1-3 except that 20.0 g of the compound(52-3) was used instead of the compound (23-1-1), 23.4 g (yield: 98.8%)of the compound (52-4) was obtained.CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)C(O)CF(CF₃)OCF₂CF₂CF₃  (52-4)

NMR Spectrum of compound (52-4):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−80(1F), −82(6F), −83(40F), −84(2F) −85(38F), −87(3F), −89(40F),−89(2F), −91(2F), −122(4F), −125(42F), −130(2F), −132(1F).

Mean value of unit number x3: 10, number average molecular weight ofcompound (52-4): 4,150.

Ex. 14-5

In the same manner as in Ex. 1-4 except that 4.0 g of the compound(52-4) was used instead of the compound (24-1-1), and the amount ofmethanol was changed to 0.34 g, 3.6 g (yield: 94.8%) of compound (52-5)was obtained.CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂C(O)OCH₃  (52-5)

NMR Spectrum of compound (52-5):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−84(40F), −89(40F), −91(2F), −118(2F), −122(4F), −123(4F), −124(38F)−125(2F).

Mean value of unit number x3-1: 9, number average molecular weight ofcompound (52-5): 3,830.

Ex. 14-6

In the same manner as in Ex. 1-5 except that 3.6 g of the compound(52-5) was used instead of the compound (12-1-1), and the amount ofH₂NCH₂C(CH₂CH═CH₂)₃ was changed to 0.46 g, 2.9 g (yield: 78.4%) ofcompound (52-6) was obtained.CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂C(O)NHCH₂C(CH₂CH═CH₂)₃  (52-6)

NMR Spectrum of compound (52-6):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(6H),3.4(2H), 5.2(6H), 6.2 to 5.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−81(2F), −83(2F), −84(38F), −89(40F), −91(2F), −120(2F), −122(4F),−125(4F), −126(40F)

Mean value of unit number x3-1: 9, number average molecular weight ofcompound (52-6): 3,960.

Ex. 14-7

In the same manner as in Ex. 1-6 except that 2.9 g of the compound(52-6) was used instead of the compound (15c-1), the amount of thexylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was changedto 0.008 g, the amount of HSi(OCH₃)₃ was changed to 0.30 g, and theamount of aniline was changed to 0.003 g, 2.71 g (yield: 99.1%) ofcompound (52-7) was obtained.CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂C(O)NHCH₂C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (52-7)

NMR Spectrum of compound (52-7):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(6H), 1.3to 1.6(12H), 3.4(2H), 3.7(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−81(2F), −83(2F), −84(38F), −89(40F), −91(2F), −120(2F), −122(4F),−125(4F), −126(40F)

Mean value of unit number x3: 9, number average molecular weight ofcompound (52-7): 4,320. The proportion of the unit (α) is 0.05 fromm2=11, m4=9 and m6=1.

Ex. 15 Ex. 15-1

Into a 500 mL eggplant flask shielded by an aluminum foil, 1.2 g ofsodium pyrithione and 50 g of 1,3-bistrifluoromethylbenzene (trade name:SR-solvent) were put, followed by stirring under cooling with ice. Then,10.0 g of the compound (52-4) obtained in Ex. 14-4 was slowly added,followed by stirring for 2 hours under cooling with ice. 2.7 g of iodineand 0.4 g of 2,2-azobis(2-methylbutyronitrile) (trade name: V-59) wereput, and the aluminum foil for shielding was removed, followed bystirring at 85° C. overnight. The temperature was returned to roomtemperature at 25° C., ethanol was added, followed by sufficientstirring, and AC-6000 was added for separation into two layers, thelower layer was recovered, and the solvent was distilled off. Theobtained crude product was purified by silica gel column chromatographyto obtain 7.9 g (yield: 85%) of compound (53-1).CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂I  (53-1)

NMR Spectrum of compound (53-1):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −55(3F),−58(2F), −81(2F), −83(40F), −88(42F), −90(2F), −116(2F), −122(4F),−125(4F), −126(38F).

Mean value of unit number x3-1: 9, number average molecular weight ofcompound (53-1): 3,820.

Ex. 15-2

Into a 50 mL eggplant flask, 7.9 g of the compound (53-1) obtained inEx. 15-1, 0.017 g of an azo initiator AIBN (trade name, manufactured byWako Pure Chemical Industries, Ltd.), 4.1 g of allyltributyltin and 7.9g of SR-solvent were put, followed by stirring at 85° C. for 12 hours.The reaction crude liquid was washed with hexane and acetone, and thelower layer was recovered. The recovered lower layer was subjected tosilica gel column, and the recovered solution was concentrated by anevaporator to obtain 6.9 g (yield: 87%) of compound (53-2).CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CH₂CH═CH₂  (53-2)

NMR Spectrum of compound (53-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.8(2H),5.5(2H), 5.8(1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −55(3F),−83(40F), −88(40F), −90(2F), −114(2F), −122(4F), −125(4F), −126(38F),−127(2F).

Mean value of unit number x3-1: 9, number average molecular weight ofcompound (53-2): 3,810.

Ex. 15-3

In the same manner as in Ex. 1-6 except that 6.7 g of the compound(53-2) was used instead of the compound (15c-1), the amount of thexylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was changedto 0.023 g, 2.38 g of HSiCl₃ was used instead of HSi(OCH₃)₃, and noaniline was used, 7.4 g (yield: 99.3%) of compound (53-3) was obtained.CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CH₂CH₂CH₂SiCl₃  (53-3)

Ex. 15-4

Into a 50 mL eggplant flask, 7.4 g of the compound (53-3) obtained inEx. 15-3 and 7.4 g of AC-2000 were put. The mixture was stirred undercooling in an ice bath, and in a nitrogen atmosphere, 10.5 mL of allylmagnesium chloride (1.0 mol/L, tetrahydrofuran solution) was slowlydropwise added. The temperature was returned to room temperature,followed by stirring for 12 hours, and a diluted aqueous hydrochloricacid solution was added, followed by sufficient stirring, and AC-2000was added for separation into two phases, the lower layer was recovered,and the solvent was distilled off. The obtained crude product wassubjected to silica gel column, and the recovered solution wasconcentrated by an evaporator to obtain 5.3 g (yield: 71.9%) of compound(53-4).CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CH₂CH₂CH₂Si(CH₃CH═CH₂)₃  (53-4)

NMR Spectrum of compound (53-4):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.9(2H),1.7(6H), 1.9(2H), 2.3(2H), 5.0(6H), 6.0(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −55(3F),−83(40F), −88(40F), −90(2F), −114(2F), −122(4F), −125(4F), −126(38F),−127(2F).

Mean value of unit number x3-1: 9, number average molecular weight ofcompound (53-4): 4,210.

Ex. 15-5

In the same manner as in Ex. 1-6 except that 2.0 g of the compound(53-4) was used instead of the compound (15c-1), the amount of thexylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was changedto 0.007 g, the amount of HSi(OCH₃)₃ was changed to 0.23 g, and theamount of aniline was changed 0.002 g, 2.2 g (yield: 99.3%) of compound(53-5) was obtained.CF₃OCF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3-1)CF₂CF₂OCF₂CF₂CF₂CH₂CH₂CH₂Si(CH₃CH₂CH₂Si(OCH₃)₃)₃  (53-5)

NMR Spectrum of compound (53-5):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.8(14H),1.6(8H), 2.1(2H), 3.6(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −55(3F),−83(40F), −88(40F), −90(2F), −114(2F), −122(4F), −125(4F), −126(38F),−127(2F).

Mean value of unit number x3-1: 9, number average molecular weight ofcompound (53-5): 4,570. The proportion of the unit (α) is 0.05 fromm2=11, m4=9 and m6=1.

Ex. 16 Ex. 16-1

In accordance with the method disclosed in Patent Document 1, Ex. 6except that the amount of methanol-added product was changed to 3 g, theamount of the compound (32-2) was changed to 5.5 g, and 1.0 g ofpotassium carbonate was used instead of potassium hydroxide, thecompound (32-2) was subjected to addition polymerization, followed bycolumn purification to obtain compound (54-1).CH₃O(CF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O)_(x3)H  (54-1)

NMR Spectrum of compound (54-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.0(2H), 4.4(18H), 6.1(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −86(6F),−91(6F), −121(4F), −122(6F), −123(2F), −126(6F), −145(3F).

Mean value of unit number x3: 3, number average molecular weight ofcompound (54-1): 1,170.

Ex. 16-2

In accordance with the method disclosed in Patent Document 1, Ex. 6,except that 6.6 g of the compound (54-1) was used instead of themethanol-added product, the amount of the compound (32-2) was changed to5.5 g, the amount of the compound (11a) was changed to 11.7 g, and 0.7 gof potassium carbonate was used instead of potassium hydroxide, thecompound (11a) was subjected to addition polymerization, followed bycolumn purification to obtain compound (54-2).CH₃O(CF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O)_(x3)(CF₂CHFO—CF₂CF₂CF₂CH₂O)_(x4)H  (54-2)

NMR Spectrum of compound (54-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.0(2H), 4.4(18H), 6.1(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −86(20F),−91(20F), −120(6F) −121(14F), −122(6F), −123(8F), −126(6F), −128(−14F)−145(10F).

Mean value of unit number x3: 3, mean value of unit number x4: 7, numberaverage molecular weight of compound (54-2): 3,110.

Ex. 16-3

In the same manner as in Ex. 1-2 except that 7.6 g of the compound(54-2) was used instead of the compound (22-1), the amount of the sodiumfluoride powder was changed to 1.5 g, and the amount ofCF₃CF₂CF₂OCF(CF₃)C(O)F was changed to 4.0 g, 8.2 g (yield: 97.9%) ofcompound (54-3) was obtained.CH₃O(CF₂CHFO—CF₂CF₂CF₂CF₂CF₂CH₂O)_(x3)(CF₂CHFO—CF₂CF₂CF₂CH₂O)_(x4)C(O)CF(CF₃)OCF₂CF₂CF₃  (54-3)

NMR Spectrum of compound (54-3):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.7(3H),4.4(20H), 4.8(2H), 6.1(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −79(1F),−81(3F), −82(3F), −86(21F), −91(20F), −120(6F) −121(14F), −122(6F),−123(6F), −126(6F), −128 (−14F), −131(2F), −133(1F), −145(10F).

Mean value of unit number x3: 3, mean value of unit number x4: 7, numberaverage molecular weight of compound (54-3): 3,430.

Ex. 16-4

In the same manner as in Ex. 1-3 except that 8.2 g of the compound(54-3) was used instead of the compound (23-1-1), 9.5 g (yield: 98.6%)of compound (54-4) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4)C(O)CF(CF₃)OCF₂CF₂CF₃  (54-4)

NMR Spectrum of compound (54-4):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−80(1F), −82(6F), −83(40F), −84(2F) −85(38F), −87(3F), −89(40F),−89(2F), −91(2F), −122(12F), −125(42F), −130(2F), −132(1F).

Mean value of unit number x3: 3, mean value of unit number x4: 7, numberaverage molecular weight of compound (54-4): 4,040.

Ex. 16-5

In the same manner as in Ex. 1-4 except that 4.0 of the compound (54-4)was used instead of the compound (24-1-1), and the amount of methanolwas changed to 0.4 g, 3.7 g (yield: 99.5%) of compound (54-5) wasobtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4-1)CF₂CF₂OCF₂CF₂CF₂C(O)OCH₃  (54-5)

NMR Spectrum of compound (54-5):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 3.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−84(40F), −89(40F), −91(2F), −118(2F), −122(12F), −123(12F), −124(−26F)−125(2F).

Mean value of unit number x3: 3, mean value of unit number x4-1: 6,number average molecular weight of compound (54-5): 3,760.

Ex. 16-6

In the same manner as in Ex. 1-5 except that 3.7 g of the compound(54-5) was used instead of the compound (12-1-1) and the amount ofH₂NCH₂C(CH₂CH═CH₂)₃ was changed to 0.47 g, 2.9 g (yield: 75.6%) ofcompound (54-6) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4-1)CF₂CF₂OCF₂CF₂CF₂C(O)NHCH₂C(CH₂CH═CH₂)₃  (54-6)

NMR Spectrum of compound (54-6):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 2.1(6H),3.4(2H), 5.2(6H), 6.2 to 5.9(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−81(2F), −83(2F), −84(38F), −89(40F), −91(2F), −120(2F), −122(12F),−125(12F), −126(28F)

Mean value of unit number x3: 3, mean value of unit number x4-1: 6,number average molecular weight of compound (54-6): 3,890.

Ex. 16-7

In the same manner as in Ex. 1-6 except that 2.9 g of the compound(54-6) was used instead of the compound (15c-1), the amount of thexylene solution (platinum content: 3%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was changedto 0.08 g, the amount of HSi(OCH₃)₃ was changed to 0.30 g, and theamount of aniline was changed to 0.003 g, 2.68 g (yield: 98.6%) ofcompound (54-7) was obtained.CF₃O(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x4-1)CF₂CF₂OCF₂CF₂CF₂C(O)NHCH₂C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (54-7)

NMR Spectrum of compound (54-7):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ(ppm): 0.75(6H), 1.3to 1.6(12H), 3.4(2H), 3.7(27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ(ppm): −56(3F),−81(2F), −83(2F), −84(38F), −89(40F), −91(2F), −120(2F), −122(12F),−125(12F), −126(28F)

Mean value of unit number x3: 3, mean value of unit number x4-1: 6,number average molecular weight of compound (54-7): 4,250. Theproportion of the unit (α) is 0.16 from m2=10, m4=6 and m6=3.

Ex. 17 to 20 Production and Evaluation of Article

Using the compound obtained in each of Ex. 13 to 16, surface treatmentof a substrate was conducted to obtain an article in each of Ex. 17 to20. As the surface treatment method, in each Ex., the same dry coatingmethod and wet coating method as in Ex. 7 to 12 were employed. As thesubstrate, chemically tempered glass was used. The obtained articleswere evaluated in the same manner as in Ex. 7 to 12. The results areshown in Table 2.

As shown in Table 2, it was confirmed that the fluorinated polyethercompound in each of Ex. 17 to 20 was excellent in the initial water/oilrepellency, abrasion resistance and light resistance.

TABLE 2 Ex. 17 18 19 20 Fluorinated ether compound Compound CompoundCompound Compound (51-8) (52-7) (53-5) (54-7) Dry Initial contact Water⊚ ⊚ ⊚ ⊚ coating angle n-Hexadecane ⊚ ⊚ ⊚ ⊚ method Abrasion resistance(steel wool) ◯ ◯ ◯ ◯ Abrasion resistance (eraser) ◯ Δ Δ Δ Fingerprintstain removability ⊚ ⊚ ⊚ ⊚ Light resistance Δ Δ ◯ ◯ Lubricity ⊚ Δ Δ ΔWet Initial contact Water ⊚ ⊚ ⊚ ⊚ coating angle n-Hexadecane ⊚ ⊚ ⊚ ⊚method Abrasion resistance (steel wool) ◯ ◯ ◯ Δ Abrasion resistance(eraser) ◯ Δ Δ Δ Fingerprint stain removability ⊚ ⊚ ⊚ ⊚ Light resistanceΔ Δ ◯ ◯ Lubricity ⊚ Δ Δ Δ

INDUSTRIAL APPLICABILITY

The fluorinated ether compound of the present invention is useful forvarious applications for which it is required to impart lubricity andwater/oil repellency. For example, it may be used for a display inputdevice such as a touch panel; surface protective coating on atransparent glass or transparent plastic member, kitchen antifoulingcoating; water repellent moistureproof coating or antifouling coating onelectronic device, a heat exchanger or a battery; toiletry antifoulingcoating; coating on a member which requires liquid repellency whileconducting electricity; water repellent/waterproof/water sliding coatingon a heat exchanger; or a surface low friction coating on the inside ofa vibrating strainer or a cylinder, etc. More specific examples ofapplication include a front protective plate, an antireflection plate, apolarizing plate, an antiglare plate or a surface thereof having anantireflection film, of a display, an apparatus having a display inputapparatus of which the screen is operated by human fingers or hands,such as a touch panel sheet or a touch panel display of an apparatussuch as a mobile phone or a personal digital assistant, a decorativebuilding material for restroom, bathroom, lavatory, kitchen and thelike, waterproof coating for a wiring board, water repellent/waterproofcoating on a heat exchanger, water repellent coating on a solar cell,waterproof/water repellent coating on a printed wiring board,waterproof/water repellent coating for an electronic equipment casing oran electronic member, insulating property-improving coating on a powertransmission line, waterproof/water repellent coating on a filter,waterproof coating on an electromagnetic wave absorption material or anacoustic material, antifouling coating for bathroom, kitchen instrumentand toiletry, water repellent/waterproof/water sliding coating on a heatexchanger, surface low-friction coating on the inside of a vibratingstrainer or a cylinder, surface protective coating on a machinecomponent, a vacuum apparatus component, a bearing component, anautomobile component, an industrial tool, etc.

This application is a continuation of PCT Application No.PCT/JP2018/019371, filed on May 18, 2018, which is based upon and claimsthe benefit of priority from Japanese Patent Application No. 2017-104731filed on May 26, 2017. The contents of those applications areincorporated herein by reference in their entireties.

The invention claimed is:
 1. A fluorinated ether compound represented bythe following formula (11):A¹-O—[(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)]—B¹  (11)wherein A¹ is a C₁₋₂₀ perfluoroalkyl group, R^(f1) is a C₁perfluoroalkylene group, R^(f2) is a C₂ perfluoroalkylene group, R^(f3)is a C₃ perfluoroalkylene group, R^(f4) is a C₄ perfluoroalkylene group,R^(f5) is a C₅ perfluoroalkylene group, R^(f6) is a C₆ perfluoroalkylenegroup, m1, m2, m3, m4, m5 and m6 are each 0 or an integer of at least 1,m1+m2+m3+m4 is an integer of at least 1, m5+m6 is an integer of at least1, and m1+m2+m3+m4+m5+m6 is an integer of from 2 to 200, B¹ is-Q[-SiR_(n)L_(3-n)]_(k), Q is a (k+1) valent linking group, R is ahydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzablegroup or a hydroxy group, n is an integer of from 0 to 2, k is aninteger of from 1 to 10, and all the (R^(f5)O) and (R^(f6)O) are locatedon the A¹-O— side from the [0.5×(m1+m2+m3+m4+m5+m6)]th unit as countedfrom the A¹-O— side.
 2. The fluorinated ether compound according toclaim 1, wherein B¹ is a group represented by any one of the followingformulae (g1) to (g7):—R^(f7)—(X¹)_(p)-Q¹-SiR_(n)L_(3-n)  (g1)—R^(f7)—(X²)_(r)-Q²¹-N[-Q²²-SiR_(n)L_(3-n)]₂  (g2)—R^(f7)—[C(O)N(R³¹)]_(s)-Q³¹-O)_(t)—C[—(O)_(u)-Q³²-SiR_(n)L_(3-n)]₃  (g3)—R^(f7)-Q⁴¹-Si[-Q⁴²-SiR_(n)L_(3-n)]₃  (g4)—R^(f7)—[C(O)N(R⁵)]_(v)-Q⁵¹-Z[-Q⁵²-SiR_(n)L_(3-n)]_(w)  (g5)—R^(f7)-Q⁶¹-G(R⁶)[-Q⁶²-SiR_(n)L_(3-n)]₂  (g6)—R^(f7)-Q⁷¹-[CH₂C(R⁷¹)(-Q⁷²-SiR_(n)L_(3-n)]_(y)-R⁷²  (g7) wherein R^(f7)is a C₁₋₆ perfluoroalkylene group, R is a hydrogen atom or a monovalenthydrocarbon group, L is a hydrolyzable group or a hydroxy group, n is aninteger of from 0 to 2, in the formula (g1), X¹ is an etheric oxygenatom or —C(O)N(R¹)— (provided that N is bonded to Q¹), R¹ is a hydrogenatom or an alkyl group, p is 0 or 1, and Q¹ is an alkylene group, agroup having an etheric oxygen atom or a silphenylene skeleton betweencarbon atoms of an alkylene group having at least 2 carbon atoms, or agroup having a bivalent organopolysiloxane residue or a dialkylsilylenegroup between carbon atoms or at a terminal on the side bonded to(X¹)_(p) of an alkylene group having at least 2 carbon atoms, in theformula (g2), X² is an etheric oxygen atom, —NH— or —C(O)N(R²)—(provided that N is bonded to Q²¹), R² is a hydrogen atom or an alkylgroup, r is 0 or 1 (provided that it is 0 when Q²¹ is a single bond),Q²¹ is a single bond, an alkylene group, or a group having an ethericoxygen atom, —NH—, —C(O)—, —C(O)O— or —OC(O)— between carbon atoms of analkylene group having at least 2 carbon atoms, Q²² is an alkylene group,or a group having an etheric oxygen atom, —NH— or a bivalentorganopolysiloxane residue between carbon atoms of an alkylene grouphaving at least 2 carbon atoms, and two [-Q²²-SiR_(n)L_(3-n)] may be thesame or different, in the formula (g3), R³¹ is a hydrogen atom or analkyl group, s is 0 or 1, Q³¹ is a single bond, an alkylene group, or agroup having an etheric oxygen atom between carbon atoms of an alkylenegroup having at least 2 carbon atoms, t is 0 or 1 (provided that it is 0when Q³¹ is a single bond), u is 0 or 1, Q³² is an alkylene group, agroup having an etheric oxygen atom or a silphenylene skeleton betweencarbon atoms of an alkylene group having at least 2 carbon atoms, or agroup having —C(O)N(R³²)—, a bivalent organopolysiloxane residue or adialkylsilylene group between carbon atoms or at a terminal on the sidebonded to (O)_(u) of an alkylene group having at least 2 carbon atoms,R³² is a hydrogen atom or an alkyl group, and three[—(O)_(u)-Q³²-SiR_(n)L_(3-n)] may be the same or different, in theformula (g4), Q⁴¹ is an alkylene group, or a group having an ethericoxygen atom between carbon atoms of an alkylene group having at least 2carbon atoms, Q⁴² is an alkylene group, or a group having an ethericoxygen atom or a bivalent organopolysiloxane residue between carbonatoms of an alkylene group having at least 2 carbon atoms, and three[-Q⁴²-SiR_(n)L_(3-n)] may be the same or different, in the formula (g5),R⁵ is a hydrogen atom or an alkyl group, v is 0 or 1, Q⁵¹ is an alkylenegroup, or a group having an etheric oxygen atom between carbon atoms ofan alkylene group having at least 2 carbon atoms, Z is a (w+1) valentorganopolysiloxane residue, Q⁵² is an alkylene group, or a group havingan etheric oxygen atom or a bivalent organopolysiloxane residue betweencarbon atoms of an alkylene group having at least 2 carbon atoms, w isan integer of from 2 to 7, and w [-Q⁵²-SiR_(n)L_(3-n)] may be the sameor different, in the formula (g6), Q⁶¹ is a single bond, an alkylenegroup, or a group having an etheric oxygen atom between carbon atoms ofan alkylene group having at least 2 carbon atoms, G is a carbon atom ora silicon atom, R⁶ is a hydroxy group or an alkyl group, Q⁶² is analkylene group, or a group having an etheric oxygen atom or a bivalentorganopolysiloxane residue between carbon atoms of an alkylene grouphaving at least 2 carbon atoms, and two [-Q⁶²-SiR_(n)L_(3-n)] may be thesame or different, and in the formula (g7), Q⁷¹ is a single bond, analkylene group, or a group having an etheric oxygen atom between carbonatoms of an alkylene group having at least 2 carbon atoms, R⁷¹ is ahydrogen atom or an alkyl group, Q⁷² is a single bond or an alkylenegroup, R⁷² is a hydrogen atom or a halogen atom, y is an integer of from1 to 10, and two to ten [-Q⁷²-SiR_(n)L_(3-n)] may be the same ordifferent.
 3. A fluorinated ether composition, comprising at least onetype of the fluorinated ether compound as defined in claim 1, and otherfluorinated ether compound.
 4. A coating liquid comprising thefluorinated ether compound as defined in claim 1, and a liquid medium.5. A method for producing an article, which comprises applying thecoating liquid as defined in claim 4 by wet coating method to a surfaceof a substrate, and removing the liquid medium, to form a surface layeron the surface of the substrate.
 6. An article having a surface layerformed of the fluorinated ether compound as defined in claim 1, on asurface of a substrate.
 7. A method for producing an article, whichcomprises treating a surface of a substrate by dry coating method usingthe fluorinated ether compound as defined in claim 1 to form a surfacelayer on the surface of the substrate.
 8. A fluorinated ether compound,which is a compound represented by the following formula (10):[A¹⁰-O—{(R^(f1)O)_(m1)(R^(f2)O)_(m2)(R^(f3)O)_(m3)(R^(f4)O)_(m4)(R^(f5)O)_(m5)(R^(f6)O)_(m6)}]_(j)—B¹⁰  (10)wherein A¹⁰ is a C₁₋₂₀ perfluoroalkyl group or B¹⁰, R^(f1) is a C₁perfluoroalkylene group, R^(f2) is a C₂ perfluoroalkylene group, R^(f3)is a C₃ perfluoroalkylene group, R^(f4) is a C₄ perfluoroalkylene group,R^(f5) is a C₅ perfluoroalkylene group, R^(f6) is a C₆ perfluoroalkylenegroup, m1, m2, m3, m4, m5 and m6 are each 0 or an integer of at least 1,m1+m2+m3+m4 is an integer of at least 1, m5+m6 is an integer of at least1, and m1+m2+m3+m4+m5+m6 is an integer of from 2 to 200, j is an integerof from 2 to 10, B¹⁰ is Q¹⁰[—SiR_(n)L_(3-n)]_(k), Q¹⁰ is a (k+j) valentlinking group, R is a hydrogen atom or a monovalent hydrocarbon group, Lis a hydrolyzable group or a hydroxy group, n is an integer of from 0 to2, and k is an integer of from 1 to
 10. 9. The fluorinated ethercompound according to claim 8, wherein in the formula (10), A¹⁰ is aC₁₋₂₀ perfluoroalkyl group, and all the (R^(f5)O) and (R^(f6)O) arelocated on the A¹⁰-O— side from the [0.5×(m1+m2+m3+m4+m5+m6)]th unit ascounted from the A¹⁰-O— side.
 10. A fluorinated ether composition,comprising at least one type of the fluorinated ether compound asdefined in claim 8, and other fluorinated ether compound.
 11. A coatingliquid comprising the fluorinated ether compound as defined in claim 8,and a liquid medium.
 12. A method for producing an article, whichcomprises applying the coating liquid as defined in claim 11 by wetcoating method to a surface of a substrate, and removing the liquidmedium, to form a surface layer on the surface of the substrate.
 13. Anarticle having a surface layer formed of the fluorinated ether compoundas defined in claim 8, on a surface of a substrate.
 14. A method forproducing an article, which comprises treating a surface of a substrateby dry coating method using the fluorinated ether compound as defined inclaim 8 to form a surface layer on the surface of the substrate.